Journal of Asian Ceramic Societies

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Development and potential of composite

moderators for elevated temperature nuclear
applications

Lance L Snead, David Sprouster, Bin Cheng, Nick Brown, Caen Ang, Edward
M Duchnowski, Xunxiang Hu & Jason Trelewicz

To cite this article: Lance L Snead, David Sprouster, Bin Cheng, Nick Brown, Caen Ang, Edward
M Duchnowski, Xunxiang Hu & Jason Trelewicz (2022) Development and potential of composite
moderators for elevated temperature nuclear applications, Journal of Asian Ceramic Societies,
10:1, 9-32, DOI: 10.1080/21870764.2021.1993592

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Group on behalf of The Korean Ceramic
Society and The Ceramic Society of Japan.

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JOURNAL OF ASIAN CERAMIC SOCIETIES
2022, VOL. 10, NO. 1, 9–32
https://doi.org/10.1080/21870764.2021.1993592

FULL LENGTH ARTICLE

Development and potential of composite moderators for elevated

temperature nuclear applications
Lance L Sneada,b, David Sproustera, Bin Chenga, Nick Brown c
, Caen Angc, Edward M Duchnowskic,
Xunxiang Hud and Jason Trelewicza
a
Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook, NY, USA; bNuclear Reactor Laboratory,,
Massachusetts Institute of Technology, Cambridge, MA, USA; cDepartment of Nuclear Engineering, University of Tennessee, Knoxville,
Tennessee, USA; dMaterials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA

ABSTRACT ARTICLE HISTORY

Neutron moderators, such as nuclear-grade graphite, are essential components of high- Received 31 May 2021
temperature nuclear reactors. Their primary functions are to degrade the energy of fission- Accepted 11 October 2021
born neutrons into an energy range that promotes further fission and to serve as the central KEYWORDS
core structure. This paper will discuss historic reactor moderator materials, which are relatively Neutron moderator; reactor;
simple monolithic materials each having intrinsic benefits and limitations. Additionally, a new composite; irradiation;
class of engineered composite moderators is presented for which two examples are fabricated: magnesia; beryllium;
magnesia-matrix composite systems with either beryllium-based or metal-hydride entrained zirconium-hydride
phases. In additions to presenting their route to fabrication effectiveness as advanced mod­
erators is discussed.

1. Introduction have ultimate plant thermal efficiency imitations

and safety concerns associated with loss-of-coolant
The study and development of neutron moderators
events. The remainder of this paper will focus on
have been central to the realization of fission power
solid moderators, and improving upon them, as
from the initial work on purification of the Chicago Pile
enabling materials for higher temperature (more
graphite. Since that early work a wide range of reactor
efficient), and potentially inherently safe nuclear
types, generally classified by coolant, fuel, and mod­
systems. Such systems, examples being gas-cooled
erator have been developed by the international com­
or fluorite-salt cooled systems, typically utilizing
munity. Recently, compact thermal fission reactors are
nuclear-grade graphite as their moderator, have
of increased interest due to their potential for lower
moderator operating temperature in the range of
and controlled construction costs, enhanced safety,
300–900°C, with some Generation IV reactors push­
and portability into remote areas. Moreover, they are
ing that temperature somewhat above 1000°C.
considered as point-sources for process industrial heat.
Moreover, these systems require their moderators
The compact nature of these cores by definition
to undergo fast-neutron damage which can have
requires good neutron economy mandating the use
a profound effect on moderator thermophysical
of a range of material solutions with low neutron
properties, almost always bad and potentially life-
scavenging and high neutron moderation. Such core
limiting. The typical neutron irradiation-induced
materials and engineering solutions need to be con­
dose (damage) to moderators depends on the spe­
sistent with long core life and high thermal efficiency
cific reactor and location within the reactor, though
to maximize plant economics.
can range from 1 displacement per atom to greater
Optimization of compact fission reactors, within
than 30 dpa. Operating at this upper damage range
limits imposed by the use of low-enriched uranium,
is beyond the useful lifetime of current solid mod­
is driven by the interplay between that fuel, core
erator materials, thus mandating change-out of
moderator, and reflector materials. Historically, core
materials.
moderator and reflector materials consist of rela­
tively simple compounds of a single material type,
with the physics of scattering favoring the lighter of 2. Materials performance of historic
the low neutron absorbing elements: H2O, D2 moderators and advanced moderators
O (heavy water), Be, BeO, C (graphite,) ZrH2, etc.
The very high density of hydrogen isotopes in Understanding the importance and then developing
water and heavy water makes for the most compact the technology necessary to purify Chicago-Pile grade
thermal reactor systems. However, such systems graphite was a major step forward in the realization of

CONTACT Lance L Snead [email protected] Stony Brook University

© 2022 The Author(s). Published by Informa UK Limited, trading as Taylor & Francis Group on behalf of The Korean Ceramic Society and The Ceramic Society of Japan.
This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/), which permits
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
10 L. L. SNEAD ET AL.

that first nuclear chain reaction. Similarly, the postula­ temperature. The continued popularity of nuclear gra­
tion of atomic displacement within the graphite crystal phite is driven both by its well understood perfor­
lattice by Eugene Wigner [1,2] and its implication to mance in nuclear systems and because it has the best
a range of performance properties including stored performance within the family of moderator materials
energy by Wigner and Szilard [3] anticipated the which demonstrate poor stability under irradiation.
importance of irradiation damage to materials. These
combined works under the Manhattan project
2.1. Graphite
founded the disciplines of nuclear materials and irra­
diation materials science. In the years and decades Nuclear graphite is essentially a composite material
following the Manhattan Project, hundreds of unique fabricated within a nuclear specification [7], incorpor­
nuclear reactor designs systems were envisioned and ating graphite coke and refined pitch products. As
built for various applications including civilian power, certain constituents are (natural) mined products and
naval propulsion, aerospace propulsion, and for civilian can moreover be manufactured in a number of differ­
and defense purposes. The choice of neutron modera­ ent ways, graphite grades are unique with each pos­
tor and reflector materials were often driven by sessing a range of both nonirradiated properties and
(experience,) application temperature, the dictated as-irradiated performance. Figure 1 provides a high-
reactor form-factor (size, mass, etc.), and the fuel burn- level description of the processing of nuclear graphite
up which relates to the irradiation damage of the core starting with the coke product, and carrying through
internals. As example, TRIGA-type research reactors a series of blending, drying, forming, and graphitiza­
operate near ambient temperature and at relatively tion steps. Nuclear graphite materials are generally
low power density and fuel burnup. As such systems distinguished by both their constituents (i.e. pitch
are not challenged by either temperature or irradiation coke or petroleum coke) and by the forming process.
damage designers opted to take advantage of the high Historically, materials such as the Sigri Great Lakes
hydrogen content of metal-hydrides, utilizing hydride- H-451 (of the Fort St. Vrain reactor) and others of that
based fuel and moderator to provide a relatively com­ era were extruded as large blocks (i.e. extruded gra­
pact and economic system. Another example for which phite.) These extruded forms tended to incorporate
compactness was a primary consideration, the Heat relatively large coke particles, in many cases utilizing
Transfer Reactor Experiment No. 3 (HTRE-3), needle cokes which led to issues of pronounced aniso­
a prototype nuclear aircraft engine, utilized yttrium tropic nonirradiated and irradiated properties.
hydride moderator and a beryllium reflector. Moreover, the extruded graphite contained relatively
A predecessor program, the Aircraft Reactor large-size pores and pronounced Mrozowski-type
Experiment, utilized BeO blocks as both the moderator cracks which formed during cool-down. In contrast to
and reflector [4,5]. At that time, both beryllium metal the extruded graphite materials, a higher degree of
and oxide were contenders, though hot-pressed beryl­ uniformity and finer grain structure is achieved
lium oxide was selected in part due to its high- through various molding processes with isostatic
temperature performance and favorable compatibility molding, a common example being the Toyo-Tanso
with dry air. Its ceramic nature, i.e. high stiffness and IG-11 graphite and IG-110 nuclear graphite. Figure 1
statistical nature of fracture, was mitigated by using provides a polished surface optical comparison of the
relatively small, segmented parts. Another program for GrafTech International PCEA Extruded graphite and
which compact architecture was a stronger driver than the Toyo Tanso Isomolded graphite IG-110. From the
fuel burnup was the Systems for Nuclear Auxiliary images the observable microstructure for the PCEA
Power (SNAP) program with the SNAP-10A reactor graphite is quite coarser with coke particles (~25 μm
tested in orbit in 1965. That system utilized for IG-110 and ~ 300 μm for PCEA) and porosity
a dispersion of uranium within zirconium hydride approaching millimeter size, while the IG-110 material
rods as combined fuel/moderator surrounded by has essentially unresolvable (by optical microscopy)
movable beryllium reflectors. Zirconium hydride and porosity on the order of tens of microns. The large
yttrium hydride continue to be a materials of choice for difference in microstructure among the graphite mate­
space nuclear systems. For larger, terrestrial systems rials can have significant impact on thermophysical
zirconium hydride has undergone performance testing properties with the isomolded graphite tending to be
as fast-breeder shield in the 21 MW KFK-2 Fast Breeder of higher conductivity and strength, though exhibiting
Reactor (FBR), with performance in canned application fracture behavior more like a fine-ceramic: somewhat
suggesting adequate performance for FBR and thermal more brittle with slightly less fracture toughness [8,9].
power reactors [6]. Interestingly, while the isomolded materials exhibit
In the larger military and commercial reactors gra­ a more uniform microstructure with less apparent
phite began and remains the moderator material of macroscopic porosity, they in fact have somewhat
choice supporting a range of significantly varying reac­ lower density compared to some extruded and vibra­
tor designs, defined primarily by the desired operating tion molded graphite owing to the higher density of
 JOURNAL OF ASIAN CERAMIC SOCIETIES 11

Figure 1. Schematic of the fabrication of nuclear graphite(right) upper left, comparison of a fuel block of a prismatic and reflector
block of a pebble-bed HTGR (upper left) [10] and comparison of microstructure of PCEA and IG-110 nuclear graphite.

very fine porosity. As example PCEA extruded graphite properties such as strength, toughness, elastic modu­
has a density of ~1.85 g/cc as compared to 1.77 g/cc lus [11,13,14], with thermal conductivity degradation
for IG-11(0). From an irradiation-damage and neutronic being the important exception, as graphite conductiv­
standpoint it is noteworthy that both materials have ity is highly sensitive the excess phonon scattering
considerable porosity, with the isomolded graphite created by irradiation-induced vacancies [15–18]. By
being nominally ~80% theoretical density (%td) while inspection of the inset crystal of Figure 1, in the typical
extruded material is closer to ~83%td. irradiation temperature of interest for nuclear systems
The performance of graphite under irradiation is of 300–1000°C neutron irradiation produces a cascade
a relatively complex interplay of evolution of the gra­ of defects, for which interstitials have the greatest
phitic constituents and the internal interfaces com­ mobility, forming new interstitial planes between the
prised of porosity and inherent microcracks. The most originally existing planes, correspondingly leaving
common description of irradiation-induced change lower mobility lattice vacancies behind. With increased
assumes the anisotropic change is dimensions of the irradiation, and exacerbated by increased irradiation
graphite crystal as the driver [11,12]. At relatively mod­ temperature, these new planes cause a dilation in the
est dose the effect of irradiation and its associated graphite crystal perpendicular to the basal planes and
volumetric compression is to improve engineering a contraction within the basal plane. As the initial
12 L. L. SNEAD ET AL.

microstructural response to irradiation is to accommo­ Examples of current nuclear application (cf.

date (annihilate) diffusing interstitials at internal por­ Figure 2) of Be block include the reflector for both
osity, the macroscopic effect is for graphite to first the High Flux Isotope Reactor and Advanced Test
densify upon irradiation. As the internal accommoda­ Reactor in the United States, and as the first wall tile
tion is overwhelmed, continued anisotropic crystal for the International Thermonuclear Experimental
swelling leads to macroscopic graphite swelling and Reactor (ITER). The most recent and most detailed
exaggerated microcracking. Typically, the point at work on beryllium for nuclear application has been
which the graphite returns to its initial volume (e.g. for the ITER project, which has selected the impact
the nil swelling point) the graphite suffers significantly ground, hot isostatic pressed S-65 C material produced
degraded thermophysical properties and has reached by Materion and a similar grade (DshF-200) produced
its useful lifetime. That neutron dose is dependent on by the Bochvar Institute. These materials are structural
temperature and to a lesser degree the nuclear gra­ grade with low (<0.1 w/0) Fe, Al, and ~1 w/% BeO,
phite grade. In the lower temperature regions of content, and guaranteed to exhibit >3% elongation
a high-temperature-gas cooled reactor (HTGR, ~300- (nonirradiated) at ambient.
500°C) nuclear graphite blocks may last for upwards of In its pure metallic form, Be has a highly anisotropic
40 dpa, while in the elevated temperature regions hexagonal crystal structure with very interesting aniso­
(~750°C) of the core where defect mobility is much tropic properties. Beryllium application has been
enhanced the dose to lifetime is on the order of 10 reviewed for fusion devices such as the International
dpa [19–21]. During that course of irradiation a typical Thermonuclear Experimental Reactor (ITER) with high-
nuclear graphite will first see mechanical properties quality materials developed, characterized, and data­
such as elastic modulus and strength increase by based [23]. A key factor limiting the use of Be, other
a more than 200 and 50%, respectively, before plum­ than its toxicity, is ductility. Be mechanical behavior is
meting while the thermal conductivity may decrease known to be a function of many factors including
by as much as an order of magnitude near 300°C and chemical purity, grain size, testing temperature, and
by a factor of about 2 near 1000°C [19,20,22]. to some extent the testing strain rate. Fundamentally,
the HCP Be crystal itself is slip resistant, severely limit­
ing flow with the only two operating slip modes (at
2.2. Beryllium metal
relevant temperatures) being basal slip on the 0001
Metallic Be has been considered for nuclear fuel planes and prismatic slip on then 1010 planes. The
compacts, cladding, and as fission reactor modera­ presence of oxygen (i.e. forming BeO) is well known
tor dating back to the early 1950s. In addition to its to impact a range of properties, but most importantly
favorable combination of low atomic mass and ductility.
parasitic absorption, beryllium provides a neutron For high purity Be, ductility can be categorized into
boost in fission power applications through its three temperature dependent regimes. On the lower
“neutron multiplier” 9Be (n, 2 n)8Be reaction. As end of nuclear application temperature (20–200°C) Be
with graphite, the Be properties strongly depend possesses two independent slip basal slip systems and
on the influence of raw materials and fabrication two independent prismatic slip systems (total 4). As
process on grain size and resultant impurity (oxy­ the Burgers vectors are normal to the basal plane at
gen: BeO) content. Properties vary significantly this temperature there is no c-component to slip. As
depending on material grade and fabrication tech­ the required five independent slip systems are not
nology [23]. While recognizing specialty optical and operative meaningful crystal plasticity is not possible
instrument grades of beryllium are known to pro­ leading to failure by transgranular fracture of the basal
vide very high quality, albeit relatively thin or small plane. Total elongation in this temperature range for
parts, for nuclear applications and in particular high quality vacuum hot pressed material (e.g. Brush
moderators only those processes resulting in rela­ Wellman S-65 C at 150°C) is ~5% in the direction
tively large parts are considered here. parallel to the pressing direction and ~20% in the
Beryllium occurs naturally as beryl Be3Al2Si6O18 and transverse direction. As the temperature is increased
chrystoberyl BeAl3O4. Figure 2 provides a high-level into an intermediate temperature regime (~200–500°C)
representation of how that ore is taken to final pro­ the critical stress for prismatic slip decreases and both
duct. As depicted, once ore is reduced to the beryllium slip modes combine to yield peak total elongations of
hydroxide starting material beryllium products may be about 50% both parallel and transverse to the forming
classified by forming process: powder metallurgy or direction due to anisotropic texturing of the grains. In
through melting and ingot metallurgy. As parts cast this intermediate temperature regime the failure is
from ingot tend to have larger grains with low and primarily ductile/fibrous tearing. In the upper tempera­
nonuniform mechanical properties the powder metal­ ture range for nuclear application (>500°C), intergranu­
lurgy process is preferred, with the most common lar failure begins to occur returning the total
forms of Be being vacuum hot-pressed block. elongation to below 20%.
 JOURNAL OF ASIAN CERAMIC SOCIETIES 13

Figure 2. Schematic of beryllium fabrication routes and examples of nuclear application.

Given the limitations to dislocation movement room temperature [30,31] where Stage IV–V
in Be, the effect of irradiation produced defects is vacancy mobility is activated above 300°C, consis­
naturally to cause further embrittlement. In the tent with the increase in void microstructure and
nuclear operating temperature range of interest helium-stabilized void swelling [32–34]. In addition
for moderators (20 to ~800°C) the homologous to defect embrittlement significant amounts of He
temperature (TM) ranges from ~19 to 68%. At the produced through the reaction 9Be(n,2 n)->2(4He)
lower end of this temperature range defect mobi­ +2(°n) also contribute to plasticity loss [35–37]. At
lity is very limited and it is expected that Be would low temperatures He is immobile in Be, but as
be significantly embrittled by defect cluster forma­ temperature exceeds ~500°C large He-stabilized
tion. Available microstructural reporting in this voids form, causing excessive swelling within Be
temperature range [24–29] discuss high density of [38]. Helium stabilized bubbles can both preferen­
small dislocation loops and black spots. Early work tially decorate and weaken grain boundaries and
on neutron irradiated Be has shown Stage II and III form within the matrix. However, in the intermedi­
interstitial migration fully available by around ate and high temperature regime the issue of
14 L. L. SNEAD ET AL.

helium-stabilized voids leading to substantial, non­ design of a high-temperature gas-cooled reactor

saturated swelling which can be design limit­ (HTGR) [40,42]. However, while considerable work
ing [39]. BeO technology was carried out that HTGR project
was ultimately canceled due to funding priorities
and the aggressive nature of the technology (at
2.3. Beryllium oxide that time.) Regardless, fundamental investigations
into the irradiation damage in the BeO system and
Beryllium oxide ceramic is a relatively high thermal
formation of BeO ceramics continued and the
conductivity material produced through any num­
material was used widely in a number of reactor
ber of powder-processing and sintering routes, not
systems. As example of progress toward process,
dissimilar to the powder metallurgy products
the Daniels Pile project routinely produced BeO
approaches depicted for Be (cf. Figure 2.) Its pro­
powders of >95.5% purity and fabricated hexago­
duction is typical of a “porcelain process” of pow­
nal moderator blocks of 15 cm in length and
der (slurry or dry) preparation, molding, and
7.6 cm across the flats. Two reactor example
sintering. BeO has found a range of boutique
nuclear applications successfully deploying BeO
applications driven by its oxidation resistance
ceramics are provided in Figure 3: (a) provides
and combined high thermal conductivity and
a top-down view of the Aircraft Reactor
operating temperature capability. Given the
Experiment, which operated in 1954 and was com­
strongly covalent nature of BeO it has a relatively
prised of pure BeO hexagonal bars (of the Daniels
high melting and sintering temperature for pure
Reactor Project vintage) through which a 53.09
powder (2570 and >1900°C, respectively). This sin­
mole % NaF, 40.73 mole % ZrF4, and 6.18 mole %
tering temperature can be suppressed through
UF4 liquid fuel was passed, and (b) providing an
addition of second phase aids such as Al2O3 or
image of the Kilopower space reactor which was
MgO, though with significantly negative impact
tested in 2018, a solid cast 93% 235U and 7% Mo
on properties such as thermal conductivity. Non-
fuel surrounded by BeO reflector.
nuclear applications include power semiconductor
Beryllium oxide suffers from a large anisotropic
devices and as structural components in high-
dimensional change in its HCP lattice for irradiation
performance microwave devices and lasers.
temperatures <800°C (~40% Tm) due to simple defect
Historically, nuclear ceramics have been fabricated
cluster formation [43]. In this temperature range, the
from pure BeO powder or from powders which
anisotropic dimensional changes rapidly lead to micro­
include minor additives such as MgO or (nuclear
cracking and significant mechanical degrading at less
grade) ZrO2, which has been used to stabilize
than 1 dpa. At nominally 600°C He forms on grain
a small-grained microstructure, added as powder
boundaries with generalized He bubble formation
sintering aids or a sol [40,41]. Development and
occurring above 800°C. Above ~35 Tm the useful tem­
study of BeO for nuclear application dates back
perature for fine-grained BeO (as defined by mechan­
almost as far as graphite, with BeO being the
ical integrity/microcracking) increases substantially
candidate reflector material (and also a core mate­
[44]. However, the substantial transmuted He is
rial) for the Daniel’s Pile, the first conceptual

Figure 3. Photographs of (a) the aircraft reactor experiment prior to reactor decommissioning and (b) the kilopower reactor under
assembly.
 JOURNAL OF ASIAN CERAMIC SOCIETIES 15

retained in the structure, with He bubbles becomes the form over a broad stoichiometric range. Two cova­
driver for unacceptable swelling [45]. At ~1100°C only lently bonded binary metal hydrides of interest to
25% of the transmuted helium is released from the nuclear are YH2-x and ZrH2-x, with LiH being an
ceramic. Insufficient quality data exists on BeO to example of an ionically bonded candidate. The
speak to the very high temperature swelling and thermophysical properties of metal hydrides are
mechanical integrity. comparable to or superior their metallic parents.
They are reasonably good thermal conductors
though markedly brittle. Relatively high values of
hydrogen to metal content (H/M ratio >1) may also
2.4. Metal hydrides
result from the Hydrogen-Induced Amorphization
The ability to stably accommodate large amounts (HIA) of refractory alloys, examples being HIA’s of
of hydrogen in metals has intriguing possibilities YFe2, GdFe2, etc [46]. As the H/M ratio along with
for nuclear applications. Metal hydrides, also the relative neutron absorption cross section of the
known as interstitial hydrides, are typically cova­ metal is key to material’s nuclear performance the
lently or ionically bonded and have the ability to stability of the hydrogen as a function of

Figure 4. Plateau pressures of hydrogen of various metal hydrides (after Vetrano [48]).
16 L. L. SNEAD ET AL.

temperature is critical. Hydrogen retention at ele­ hydrogen partial pressure informed with the well-
vated temperatures requires specific attention to established PCT map gives rise to the desired hydro­
develop hydrogen barriers for the metal hydride. gen concentration in as-fabricated hydride. The
Figure 4 provides an overview of hydrogen contain­ needed shape and dimension of the hydride pieces
ing materials of interest and in particular plateau pres­ may be achieved without additional machining if the
sure (the partial pressure of hydrogen above a two- starting metals are carefully designed based on the
phase metal-hydrogen solid) for a number of binary expected volume expansion in the hydriding process.
metal hydrides. Also provided with Figure 4 is the Large-scale metal hydride may also be fabricated via
specific hydrogen density of each material in atoms the powder sintering route, starting with the high
of hydrogen per cm3, which can be compared with purity hydride powder. It is noted that the sintering
that of water (6.6×1022 H a/cm3). process needs to be in the low temperature regime to
Fabrication of the transition metal hydrides such as avoid significant hydrogen release, altering the H/M
YH2-x and ZrH2-x can be accomplished through ratio. In addition, the sintering process is cumbersome,
a number of routes. However, (direct or-) massive as it involves multiple handling and processing steps,
hydriding and sintering of base hydride powder are requires handling metal hydride powder in inert glove
the two most common routes, each with benefits and boxes, for which care is required to avoid introducing
drawbacks dependent on the application of interest. impurities in the hydride. Typically, massive hydriding
The term massive hydriding was coined to differentiate allows fabrication of more complex geometries as
this process from the classic sintering approach which compared to the sintered product.
has defined geometric part size limits based on the Examples of direct hydride articles are provided in
tooling utilized (i.e. sintering die.) While typical sinter­ the upper image Figure 5, with an early and famous
ing geometries are on the order of a few to tens of cm example of hydride, the SNAP-8 space reactor [49]
in any dimension, massively hydrided parts can be provided in the lower image. Neutron irradiation
substantially larger, limited by the size of the reaction response of metal hydride has not been significantly.
chamber. In the early development of YH2-x for space In 1960s, the hydride Y-5%Cr alloys cladded with Fr-
reactor application typical massively hydride parts 20Cr-4.5Al was irradiated in a nuclear reactor environ­
were 30–40 kg with dimension greater than 100 cm ment at 700°C and 1000°C for 1950 and 2450 hours in
[47]. In massive hydriding the exothermic hydriding air, respectively. All irradiated specimens remain intact
reaction is taken advantage of through typically slow without weight or dimension changes. Hydrogen con­
and controlled reaction with hydrogen to avoid part- centration change was also seen to be negligible [50].
cracking. Besides this study, there is no additional literature data
Fabrication of metal hydride through direct hydrid­ on the neutron irradiation impact on the thermome­
ing can be done in a variety of ways: such as introdu­ chanical properties of yttrium hydride. As to zirconium
cing a measured amount of hydrogen into retort or hydride, the growth of U-ZrH fuel during irradiation
carefully matching retort temperature and hydrogen has been studied extensively in the SNAP reactor pro­
pressure. Massive metal hydride fabrication is usually gram. Dimensional change is dependent on the
achieved using the latter method. The M-H binary burnup, ranging from 0.6% to 1.4% at 760°C [51].
phase diagram and the pressure-composition- Some other irradiation experiments indicate negligible
temperature (PCT) map are the two most important change in the density of ZrH1.7 after irradiation to
pieces of information needed to guide fabrication of fluences of 7 × 1020 to 1.1 × 1021 n/cm2 (E > 1 MeV,
metal hydride. Hydriding is a rate-controlled exother­ just under 1 dpa) at temperatures up to 570°C [52].
mic process. The rate limiting process may be diffusion
of hydrogen inside the solid metal or hydride, as H is
3. Development of composite moderator
supplied to the solid or surface adsorption, depending
systems
on the bulk H2 gas flux onto the surface. The most
significant challenge in fabricating massive crack-free Moving beyond the historic moderators discussed in
bulk metal hydride (or during rapid dehydriding) is the previous section, engineered materials are an
that if the hydrogen concentration gradient across option for moderator and reflector application.
the sample body is not managed to a low value, then A number of example composite materials and
differential lattice strain results lead to significant advanced manufacturing techniques may be consid­
stress. This stress, coupled with the low fracture tough­ ered aligned along certain principles including the
ness of the hydride materials, is the ultimate source of need for acceptable neutronics, environmental stabi­
cracking and it is routinely exploited to produce pow­ lity, fabricability, and economic viability of the material
der from various metals in the hydride-dehydride pro­ system as applied to design. One conceptually simple
cess. Slow hydrogen flow rate coordinated with the system is a multiphase composite, where a highly
high processing temperature yields the crack-free moderating entrained phase is contained within
metal hydride. Matching the retort temperature and a continuous and environmentally stable matrix
 JOURNAL OF ASIAN CERAMIC SOCIETIES 17

Figure 5. (a) Photographs of as-fabricated yttrium hydride and zirconium hydride through direct hydriding. (b) A systems nuclear
auxiliary power (SNAP)-8 nuclear reactor core, showing some of the cylindrical U-ZrHx fuel elements, clad in a nickel-steel
superalloy. The core is approximately 20 cm in diameter [49].

phase. The conceptual architecture for such envisioned, some of which could be designed to simul­
a composite, and in particular the desired attributes taneously enhance engineering properties of interest
for a composite moderator are provided in Figure 6. such as thermal conductivity (as example, through
Such a random or ordered two-phase composite is one nonuniform incorporation of high-conductivity fibers)
of many types of composite forms which could be or enhancing strength and fracture toughness (as
18 L. L. SNEAD ET AL.

Figure 6. Conceptual figure and constituent attributes for a composite moderator.

example through a composite architecture based on entrained phases are provided in Table 1 below, focus­
whisker, platelet, or fiber reinforcement.) Moreover, ing on thermally stable compounds of high density,
such a composite should be contrasted with nuclear low-atomic numbered constituents. As neutron mod­
graphite is arguably also a composite material of simi­ eration is physically described by simple elastic “bil­
lar architecture (coke particles in a continuous matrix liard-ball-type” collision, the most efficient entrained
of binder-derived graphite), though a differentiation phase moderators possess high densities of elements
being made here is that this engineered two-phase with mass approaching that of a neutron: H, Li, Be, B,
moderator has a matrix phase selected for its structural C . . . Along with the logarithmic energy decrement ξ,
integrity, in contrast with the relatively weak and the atomic mass and number density of elements in
unstable matrix of nuclear graphite. a material determined the slowing down power,
A wide array of matrix and entrained phases exist a primary metric for comparing the effectiveness of
for the engineered two-phase moderator. As the materials as moderators: Slowing Down Power = ξ Nd
fundamental goal is to arrive at a bulk material σs, where Nd is the atomic number density and σs is the
that is structurally and neutronically superior to cross-section for neutron scattering. In Table 1 and
nuclear graphite, a sensible metric is that the result­ Figure 7 the slowing down power of potential
ing composition having a rule-of-mixtures slowing entrained phases are compared to the two most com­
down power (to be discussed) comparable to or mon moderators, graphite, and water. As seen, the
exceeding that of graphite. Of the common oxide, slowing down power for water far exceeds that of
nitride, and carbide-based structural ceramics a few graphite, owing the very high density of low atomic
candidates warrant immediate attention. number hydrogen. For this reason, light-water-reactors
(LWR’s) enable relatively small and very high-power
density cores, especially as compared to the higher
3.1. Entrained phases of a two-phase composite temperature graphite-moderator gas-cooled systems
moderator for which the materials in this work are being devel­
As the in service thermal and mechanical property oped for.
requirement of an entrained phase are relatively unim­ Beyond simple moderation, neutron scavenging
portant (see Figure 6) material selection is relatively becomes very important, with the thermal neutron
straight forward focusing on materials processing absorption (σa) of constituent elements provided in
issues, benefit to overall moderation with minimal Table 1. This is typically quantified as the Moderating
neutron scavenging, and susceptibility to environmen­ Ratio: ξ Nd σs/σa. For these metrics of neutron scatter­
tal degradation. In this application environment effects ing and absorption it is clear why the historic modera­
include long-term thermal stability under irradiation tors graphite, beryllium, and beryllium oxide were
and the potential interaction of the entrained phase chosen. Each is of high scattering due to its high
with the host matrix. An abbreviated list of candidate density of light atoms and each possesses a relatively
 JOURNAL OF ASIAN CERAMIC SOCIETIES 19

Table 1. Property comparison for composite moderator entrained phases.

Slowing
down Thermal neutron absorption Tmelt
power Theoretical number cross-section barns σa Tdecomp ρth Irrad. perf, Kth
ξ Nd σs density limit on H or Be [primary isotope/ TPlat Pres (g/ Chemical (~500°C, >20 (@~650°C)
(1/cm) (1022 a/cm3) average] °C cc) reactivity Crystal dpa) W/m-K
Graphite 0.079 - C: 0.0035 >(3000) 1.8 O2:Rx@>800 C Hexag. Poor ~20
Water 2.63 6.6 H: 0.333 1
O: 0.00019
Be 0.195 12.4 0.0076 1287 1.85 O2:Rx@>500 C Hexag. Bad ~60
BeO 0.151 7.27 Be: 0.0076 2507 3.015 Very low Hexag. Very Bad, ~30
O: 0.00019 anisotropic
Be211B 0.160 7.86 Be: 0.0076 1504 1.89 Cubic Unknown Unknown
B: 0.0055/3835
Be411B 0.102 9.9 Be: 0.0076 1160 1.94 Tetrag. Unknown Unknown
Be2C 0.103 9.6 Be: 0.0076 1600– 2100°C 2.4 N:
C: 0.0035
Rx@>1100 C Cubic Limited ~22
O2:Rx@>800 C [53] [70]
ZrBe13 0.161 10.2 Zr: 0.011/0.185 1525 2.72 Cubic unknown ~40
Be: 0.0076
TiBe12 0.147 10.4 Ti: 7.84/6.49 1925 2.26 Hexag. Poor, 1%@5
Be: 0.0076 dpa
VBe12 10.8 V: 4.9/5.08 1700 2.37 Hexag Unknown
Be: 0.0076
11
B4C 0.123 - 0.0055/3835 2350 2.52 Rhomb. Unknown ~12–15
LiH 1.2 5.8 Li: 0.045/940 0.78 Cubic
H: 0.333
CaH2 5.47 Ca: 0.41/0.43 Rhomb
H: 0.333
SrH2 4.42 Sr: .058/1.28 1050 3.26 Water reactive Rhomb
H: 0.333
Ti H2 1.85 9.1 Ti: 7.84/6.49 3.78
H: 0.333
ZrH 2-x 4.75 5.8 Zr: 0.011/0.185 ~600– 5.66 Cubic Bad at high 16–18
H: 0.333 900 dose/T
ZrD 2-x 5.8 Zr: 0.011/0.185 ~600– Cubic
D: 0.0005 900
YH 2-x 4.64 5.68 Y: 1.28 ~800– 4.293 Cubic Bad at High 8.2
H: 0.333 1100 dose/T
(largely
unknown)

Figure 7. Slowing down or moderating power for potential moderators.

low neutron absorption cross section. Moreover, the neutron absorption cross sections. The classic example
naturally occurring unstable isotopes of these ele­ of this is boron, which has an average neutron absorp­
ments all possess low absorption. This is in contrast tion cross-section of 767 barns (1 barn = 1×10−24/cm2),
with a number of materials of interest for which natu­ though the absorption of the two naturally occurring
rally occurring isotopes can have vastly different are substantially different: 10B isotope having
20 L. L. SNEAD ET AL.

a naturally occurring abundance of 20% and a cross Like beryllium-boron, Lebeau is also credited for the
section of 3835 barns while the majority (80%) discovery and early work on beryllium carbide, Be2
11
B isotope has a relatively small cross section of C [62,63]. Unlike the beryllium-boron system, Be2
0.0055 barns. This is captured in the table with the C with its cubic structure is the only phase that exists
primary isotope and average isotope cross sections in the Be-C system. It is both a very hard and abrasive
listed separately. Another example important to the material with density as determined through bulk den­
nuclear industry are the isotopes of hydrogen, with sity measurement [64,65] and X-ray [66,67] of 2.44 g/cc,
1
H having a neutron absorption of 0.333 barns in com­ though it is noted that in early work on the mass
parison to the much reduced 0.0005 of 2D (deuterium.) production of Be2C [68] a much reduced density was
This disparity is why heavy water was (along with reported, likely due to inclusions of graphite and high
purified graphite) the two original moderating materi­ levels of BeO present in the compacts. This lower,
als utilized to determine the possibility of the fission incorrect density has unfortunately been propagated
chain reaction. For the purposes of Table 1 and in through online resources such as MatWeb, Wikipedia,
discussion of potential entrained phases for moderat­ and the Compendium of Material Composition Data
ing composites it is important to note that isotopic for Radiation Transport Modeling [69].
tailoring, or the separation and use of certain low In Lebeu’s original work two generic methods of
absorbing isotopes, is a known technology, albeit forming Be2C were the reaction of Be metal or reduc­
potentially costly. As example, deuterium is commonly tion of BeO with “sugar charcoal.” While the reaction of
separated for use in heavy water reactors and BeO at high temperature has been pursued as
10
B isotope is routinely separated from natural boron a potential more commercial process [64,68] the for­
for nuclear application leaving the reduced cross- mation and sintering of pure powders appears to result
section 11B isotope behind as by-product. in higher quality product. It is noted that direct reac­
While technically feasible, and noting the rela­ tion of Be metal with graphite powder, which reacts
tively attractive slowing down power of the beryl­ exothermically upon reaching 900°C, is another viable
lium borides of Table 1, these materials are not option. As Be2C reacts with moist air progressively
pursued here essentially because the potential cost hydrolyzing to form Be(OH)2 consolidation is best car­
impact of isotopic tailoring. However, a number of ried out in inert environments. A number of standard,
materials in the B-Be family have attractive slowing dry, powder ceramic techniques are possible and result
down powers, and absent 10B, have attractive mod­ in fully dense ceramic [64,65]. In the bulk Be2C is not
erating radio. While the first identified phase of attacked by moist air, but due to its significant reaction
beryllium boride was made by Lebeau in 1896 [54] with nitrogen above 1100°C and by oxygen above
the earliest report discussing the processing of the 800°C it has not receive commercial application. It is
Be-B system with corresponding structure identifica­ noted that these environmental conditions may not be
tion was carried out by Markovskii et al in 1955 [55]. of concern in certain moderator application. Finally,
There, reaction was carried out Be-B reaction in the irradiation stability of Be2C is essentially unknown,
a range of 20:1 to 1:6 in vacuum and hydrogen with the only known study carried out below 90°C to
from 1300 to 1400°C, with identification of BeB6. a fluence of less than 0.01 dpa (3.5 × 1022 n/m2.) [70]
As has been made apparent since that time, in the Little physical property change was noted at this very
Be-B family a range of materials occurs, from Be-rich low fluence.
to B-rich phases with some stable at the intermedi­ Beryllium intermetallic compounds (beryllides),
ate to high temperature considered here. However, examples listed in Table 1 being ZrBe13, TiBe12, and
the only Be-rich phase that appears to be stable at VBe12, have received sporadic interest from the funda­
room temperature is Be4B. On the boron-rich side mental materials science, nuclear fission, aerospace,
a BeB2, BeB3, BeB4, and BeB6 have been described and nuclear fusion communities over several decades
[56–61], though study has been somewhat limited [71–78]. Apart from their exceptional high temperature
and in fact controversy still exists as to whether mechanical properties, the relatively high Be number
BeB2 exists, or is in fact a more complex structure density gives them very attractive moderating poten­
such as BeB2.75 [57]. These beryllium borides have tial. In particular, the slowing down power of ZrBe13
never been studied in a serious way for nuclear falls between that of Be metal and BeO. While all the
application, with interests being either purely scien­ beryllides will have a lower moderating ratio than Be or
tific or in support of light armor or other light- BeO given the higher thermal neutron absorption
weight, high stiffness application. Currently, there cross section of the metal (Zr, Ti, or V), the ZrBe13 in
exists no data on irradiation stability of this family particular possesses a relatively low neutronic penalty
of materials with little information on its reaction as compared to BeO. Potential advantages of the inter­
with water or air at elevated temperature. However, metallic systems as compared to BeO are their higher
it would be assumed that formation of beryllia as-irradiated thermal conductivity and overall irradia­
would provide some level of protection. tion stability. However, as a family the understanding
 JOURNAL OF ASIAN CERAMIC SOCIETIES 21

of the irradiation stability is poorly studied, with only Metal-matrix, intermetallic-matrix, and ceramic-
limited information on the TiBe12 available [79,80]. In matrix composites may be considered as advanced
the recent work of Federov [80] in the 145°C-725°C moderators. However, within the limitation of tem­
range and doses to 1.4 × 10 26 n/m2 (E > 0.1 MeV) (a perature and neutron absorption metal-matrix candi­
dose and temperature range of relevance for modera­ dates are extremely limited. Be-metal is conceivable,
tor application), materials exhibited a few percent iso­ though for the upper-end of the desired temperature
tropic swelling and phase stability. As comparison, at and dose regime irradiation swelling and embrittle­
that dose and temperature the anisotropic dimen­ ment are significant issues. Other, low neutron absorb­
sional change of BeO would have led to severe micro­ ing metal such as Al and Mg soften and melt within the
cracking and loss of strength and Be metal would incur desired application temperature range, could be con­
unacceptably high swelling. sidered at low temperatures. Intermetallic matrices
Through entrainment in a dense composite matrix offer the potential for higher temperature application,
which would inhibit decomposition, hydrides offer tre­ though of the most commonly developed alloys none
mendous potential to significantly enhance neutron is neutronically acceptable. Less well-developed inter­
moderation. As discussed in Section 2, the technology metallic systems, such as the select beryllium interme­
of forming monolithic metal hydride parts of high tallics such as ZrB12 (cf Table 1) and potentially
quality has been established and a technology readi­ materials in the Mg- and Ca-based systems have
ness level established for their use in reactor. However, potential.
safety and performance limitation with regards to ther­ Ceramic matrices appear to offer the most potential
mal and irradiation-induced loss of hydrogen. for high-temperature composite moderator applica­
Referring to Figure 4 a large number of metal hydrides tion. Many offer reasonable neutron moderation as
of sufficient thermal stability to be considered as com­ well as acceptable neutron absorption and high-
posite entrainment materials, depending ultimately on temperature performance. The most well studied
the processing conditions. Table 1 provides a list nar­ example is SiC, which can be matrix-processed using
rowed by considering the absorption cross section of a wide range of methods, though from an irradiation
the metal. As seen, the hydrogen density is relatively stability point of view [81–84], matrices processed
close for the selected metal hydrides with TiH2 being at either by chemical vapor infiltration (CVI/CVD) or
the upper end of the spectrum. However, while TiH2 is through a transient-eutectic sintering process appear
often considered for nuclear application the relatively the most promising. While processing temperature to
large absorption cross-section argues against its use. achieve a full density matrix can be below 1800°C
[85,86], the neutron scavenging of Si (cf Table 1) ren­
ders SiC less than attractive as a moderator. Higher
3.2. Matrix phases of a two-phase composite thermal conductivity ceramics such as Si3N4 and AlN
moderator can be similarly excluded. Glass shares the same issue
Referring again to the composite schematic of of Si neutron absorption but should also be ruled out
Figure 6, the fundamental difference when selecting based on the fundamental irradiation-instability of the
a matrix material for a two-phase moderator as com­ structure [87,88]. However, glass ceramics in the ZAS
pared to the entrained phase is the additional thermo- (ZnO × Al2O3 × nSiO2), LAS (Li2O × Al2O3 × nSiO2), and
mechanical performance requirements and in some MAS (MgO × Al2O3 × nSiO2) assuming marginal neu­
cases the need to retain hydrogen. As envisioned, the tron scavenging can be tolerated and isotopic tailoring
matrix phase would be the primary load-carrying con­ for the case of the lithium. It is noted that known
stituent of the composite, where the primary load compositions do include glass ceramics with reduced
existing in classic graphite stacked-block gas-cooled Al and Si concentration. (For example, GOX glass cera­
reactors is compressive, with both fracture toughness mic based on parent glass composition 39.5SiO2
and tensile strength becoming important as the struc­ -1255Al2O3-21.5Cao-12.5 Mg)-12.5Y2O3-1.5ZrO2.) [89]
ture evolves under irradiation-induced dimensional Limited data on irradiation performance of glass cera­
change. As such stresses are compounded by thermal mics suggest a level of stability [90].
gradients the desire for higher conductivity (as irra­ Stabilized ZrO2 and Al2O3 are indifferent performers
diated) is also of importance. As mentioned in the neutronically, though both have excellent high-
introduction the application temperature range of temperature stability in a range of environments with
interest can range within a typical graphite moderated Al2O3 being relatively stable under irradiation [45,91]
gas-cooled reactor from 300 to 900°C or higher. This and ZrO2 less so [92,93]. However, the high coefficient
temperature, combined with the need for very low of thermal expansion (11 x 10−6 /K) of ZrO2 combined
neutron absorption (typically σa<0.1 barn for a low- with it extremely low thermal conductivity makes it
enriched-uranium thermal spectrum reactor) defines a poor choice as a block moderator material. The con­
the potential matrix materials. ventional sintering of polycrystalline pure Al2O3 is
22 L. L. SNEAD ET AL.

a grain boundary diffusion limited process beginning through application of pressure and by moving toward
at approximately 1400°C and reaching near full density smaller and purer powders including nanopowder. As
at around 1700°C [94]. Various approaches in powder example >99% theoretical density can be achieved,
processing including high-purity and finer power, sin­ with restrained grain growth, by application of rela­
tering aids, and the application of spark plasma sinter­ tively high pressure (170MPa) and by using nanopow­
ing can be used to reduce the temperature at which der [108] at 1470°C. Use of spark plasma sintering
a dense compact by a few hundred degrees Celsius enables grain growth control, providing a more ther­
[95,96]. Techniques such a spark plasma sintering of mal shock resistant ceramic, by inhibiting grain growth
pure alumina powder and powder including sintering through a rapid heating stage leading to final sintering
aids demonstrate dense ceramic at 1300°C [97,98]. [108]. Further suppression in sintering temperature can
Given the reasonable scattering and extraordinarily be achieved through the use of elemental sintering
low neutron absorption of Mg, the family of refractory aids such as Al, Cr, Fe, Mn, V, lithium-bearing salts
oxides containing magnesium are of particular inter­ [109] and various oxides [110]. Compounds such as Li-
est. MgAl2O3, or Magnesium Aluminate spinel (Ma) bearing salts [111,112] and oxides such as TiO2 [110]
while a relatively weak ceramic, is known for its high- have also been shown to produce relatively low-
temperature use and irradiation stability, being widely temperature full-density ceramic [109,113]. With
used as refractory brick in kilns, ladle lining in steel­ regards to irradiation stability the database for dense
making, and having been variously studied as a fuel MgO ceramics is not comprehensive, though existing
matrix and waste form material [45,91,99–101]. As data [91,100] suggest good dimensional stability under
there is limited natural occurring MA the ceramic is irradiation in the temperature range of interest to
typically formed through solid state reaction of MA- moderator (300–900°C.) As example Clinard [91], in
bearing precursors such as Al2O3 and MgO, which are comparing the irradiation swelling of Al2O3 with MgO
readily available. Direct sintering of commercially pro­ find MgO to swell to ~ 3% by 30 dpa while alumina
duced MA powder is common, through the usual pro­ exhibits ~6% swelling. This can be compared with
cesses of hot-pressing, hot-isostatic pressing, spark nuclear graphite at a similar dose and temperature,
plasma sintering, etc. though given the availability which would have initially densified in excess of 5%
and purity of Al2O3 and MgO, the precursor powder and then reversed to swelling behavior and cata­
route is preferred [102]. Importantly, a significant strophic loss of mechanical properties [20]. Moreover,
volume change (~8%) occurs during MA formation, due to the cubic (Fm3m rocksalt) crystal structure of
leading to a usual dual stage sintering in the 1000– MgO the lattice undergoes isotropic expansion as com­
1600°C range which increases cost. pared to the undesirable anisotropic expansion and
Due to the presence of Al the overall absorption of related stress-induced reduction in strength of gra­
MgAl2O3 may not be ideal for some moderator appli­ phite, BeO, and Al2O3.
cation. In contrast, magnesia (MgO) is a superior neu­
tronic candidate as both elements Mg and O (cf
3.3. Neutronic impact of proposed two-phase
Table 1) have very low cross sections and the overall
composite moderators
slowing down power is ~55% that of graphite, provid­
ing the composite a moderating boost from the matrix In the following sections demonstrations of two-phase
to compliment the entrained phase. To this point there moderators, composed of materials discussed in the
has been little discussion of MgO as a bulk moderator preceding sections, are described in some detail.
[103] though it has been discussed as both inert matrix However, prior to that materials description it is
for nuclear fuel [104–106] and as a waste form barrier instructive to demonstrate the potential neuronic per­
material [107]. MgO ceramics have widespread com­ formance for these systems. Table 1 provides insight
mercial application, as a primary crucible material and into both slowing down power and moderating ratio,
a number of other common uses such as construction perhaps the two most important metrics for
flame resistant fireboard. It is one of the most studied a moderating material. However, as the materials
refractory ceramics with an extensive database with being discussed are essentially neutronically tunable
example applications dating to the Great Wall of through selection and volumetric fraction of their con­
China and early Roman construction. Final form mate­ stituents and in many cases, it is possible to over
rials vary widely, including fibers, porous structures, moderate a system, it is ultimately important to engi­
composite, and sintered bodies of varied density. For neer one or more moderators for each specific reactor
discussion purposes and related to reactor moderator or reactor type. Regardless, the most simplistic descrip­
application materials and processes for densities in tion of the effectiveness of the suggested composite
excess of 98% are desired. moderator is made by determining the critical volume
Sintering of pure MgO powder into dense ceramic is of a sphere, where the fuel is homogeneously dis­
readily achieved at temperatures in the sintering range persed within the moderator and the sphere size
of 1200–1650°C, with lower temperatures achieved required to reach “reactor” criticality is estimated. This
 JOURNAL OF ASIAN CERAMIC SOCIETIES 23

is provided in Figure 7. In this simple example moderators also have a softer neutron spectrum
a number of selected MgO-matrix composites result which leads to less radioactivity per unit energy
in significantly smaller critical volumes as compared to generated which is expected to reduce the shield­
nuclear graphite, with the MgO-15% ZrH1.6 have under ing and long-term storage requirements of the
half the required volume. The MgO-matrix composite spent nuclear fuel. Calculations of critical core size
entrained with either Be or BeO also show significant were performed for a hypothetical nonreflected
benefit, while the SiC-matrix, due to the greater neu­ homogenous spherical reactor showed that the
tron absorption of the Si atom, has poor performance. most promising composite moderators, that con­
For similar reasons composite moderator fabricated sisted of a MgO-matrix composite entrained with
from MgAlO4 and Al2O3 are less attractive than the either hydride, Be, or BeO, provided a smaller size
MgO-based moderators. than for graphite moderated system, also illustrated
Clearly, the composite moderators have in Figure 8.
a potentially large and beneficial impact on core Thermal-hydraulic safety calculations were also per­
size and associated uranium loading, though the formed in the aforementioned study for the most pro­
enhanced moderation can lead to serious conse­ mising beryllium-based composite moderators. The
quences on reactivity coefficients and other impor­ beryllium-based moderators have a lower thermal con­
tant safety and performance parameters and must ductivity but higher volumetric heat capacity than that
be carefully examined. Such work has been carried of graphite. Calculations showed that for accidents
out (REF including thesis?) whereby composite that result in an absences of active core cooling, no
moderators are considered as direct replacement moderated system is expect to compromise the fuel.
into a well-studied modular high-temperature gas- The differing thermophysical properties of the beryl­
cooled reactor (mHTGR) configuration previously lium-based moderators to graphite results in a lower
optimized for nuclear graphite. In that detailed fuel temperature increase but longer times at elevated
work, assembly level calculations were performed temperatures.
for composite moderators to evaluate performance
and compared against a graphite moderated sys­
tem. The analysis showed that the composite mod­ 3.4. Fabrication of MgO-matrix two-phase
erators could provide similar or enhanced cycle composite moderators
performance relative to graphite. The improved 3.4.1. Reduced temperature MgO processing
cycle performance results in lower fuel cycle costs Magnesia has been relatively widely studied as
and a lower environmental impact for the compo­ a second (entrained) phase material additive, whether
site moderators relative to graphite. The composite in particle or whisker form, for a number of ceramic

Figure 8. Core critical volume of a nonreflected sphere of various composite moderators of optimized fuel/moderator ratio
including a uniform distribution of TRISO fuel (e.g. UCO, enrichment = 15%).
24 L. L. SNEAD ET AL.

and alloy-matrix composites. However, there has been below any reaction or melt/disassociation limits of the
little interest in dense MgO as composite matrix, likely entrained phase. Reduction of sintering temperature,
due to the relatively low strength and fracture tough­ time, and pressure is therefore of interest.
ness of the ceramic. Some published works explore the For the present work sintering of powder with
MgO-Al2O3 (a spinel precursor) [114,115] system, MgO a single or bi-modal particle size distribution was
as matrix for inert-matrix nuclear fuels [104], and as carried out using direct current sintering, schemati­
composite with SiC reinforcement in fundamental oxi­ cally shown in Figure 9. For single particle size
dation studies [116]. As discussed in Section 3.2 dense distribution an 99.9% purity powder of < 5 microns
magnesia ceramic is achieved through a wide array of is effective. Sintering temperature was suppressed
high-temperature sintering techniques, with a number through appropriate selection of size and purity of
of processing routes and formulations effective to MgO powder and the use of a lithium-bearing salt
reduce sintering temperature and controlling grain additive (>99.9% pure) at 1%. Salt-bearing powders
size. Of primary interest for MgO-matrix moderators is pre-mixed and cold pressed a nominal sintering
the achievement of a high-density matrix processed applied pressure of 10 MPa resulted in a much-

Figure 9. Schematic describing the lithium-salt assisted direct current sintering of MgO composite with entrained phases of Be
metal, BeO, Be2C, or ZrHx (or YHx).
 JOURNAL OF ASIAN CERAMIC SOCIETIES 25

reduced temperature (cf Figure 9) for both onset of with the majority of densification occurring by
sintering and temperature required to achieve full 850°C. For this reason, and for the remaining dis­
(>98% theoretical MgO) density. Specifically, at the cussion in this paper, 10 MPa applied pressure is
1% additive level LiCl, LiBr and LiF reduced the assumed.
sintering onset temperature from ~ 1070°C to Beyond the demonstrated efficacy of the Li-bearing
~890°C (LiCl), ~860°C (LiBr), and ~ 740°C (LiF) salt in suppressing sintering temperature, selection of
[117,118]. Full density (>98% theoretical) was this sintering route has a clear advantage insofar as the
achieved at 1030°C for the MgO-1% LiF and salt is a fugitive sintering aid: according to previous
1200°C for the MgO-1%LiBr. At the upper sintering work [119] in the Al2O3-LiF system it would be
temperature of 1200°C the LiCl and pure MgO expected that LiF evaporates from the system at
achieved ~97% theoretical density. From Figure 9 approximately 845°C. This was demonstrated through
it is noted that for the MgO-1% LiF there is a weak a series of increasing temperature sintering studies of
dependence of final density on applied pressure, MgO-1%LiF as shown in Figure 10. Referring to the

Figure 10. Evaporation of the LiF as demonstrated through analysis of MgO-1% LiF ceramic X-ray patterns at 900°C, 1000°C, and
1100°C.
26 L. L. SNEAD ET AL.

topmost scan of the figure, which provides (as blue The in situ XRD patterns are shown in Figure 11(a) as
squares) the 45° and 65.2° location of the diffraction a function of temperature (up to 871 K). The initial
peaks. With increasing sintering temperature both of phases in the powders are LiF, MgO, and Mg(HO)2.
these peaks diminish substantially with the 65° peak After 572 K, the Mg(HO)2 phase decomposes. Note
disappearing as a result of the 1100°C sintering. SEM/ that a minor phase (currently unidentified) is observa­
EDS analysis confirms the absence of LiF in this 10 μm ble at 519 K onward, with subtle peaks at two-theta
grain size sintered MgO. 6.63 and 5.35 degrees. The change in the positions of
As discussed in section 3.2 a range of sintering aid the XRD peaks for the LiF and MgO to lower two theta
additives have been shown effective to enhance low- positions with higher temperature is indicative of ther­
temperature sintering of MgO. The physical mechan­ mal expansion and/or defect formation. Figure 11(b)
ism for this impressive shift in the sintering tempera­ shows the lattice parameter for MgO determined from
ture window (~350°C) is, at the present time unknown. the quantitative Rietveld refinements as a function of
Previous works have speculated that LiF acts as an temperature, with reference MgO shown as red sym­
accelerant to the sintering process, either through bols [127]. The clear deviation in the elevated tempera­
the formation of a reactive liquid phase that “wets” ture lattice parameters for the MgO + LiF mixture,
the surface of MgO grains, or through a plastic defor­ compared to the MgO reference, indicates that
mation process [109,111,120–122]. Based on our initial a substantial higher point defect population must
results and these past works, we speculate that the Li exist. The temperature at which the deviation occurs,
dopants form complex phases with the MgO enhan­ ~500 K, is well below the decomposition of the
cing surface diffusion and sintering. To test this Mg(HO)2 and LiF phases (572 and 1100 K, respectively),
hypothesis, we performed in situ high energy x-ray and intriguingly close to the onset of the formation of
diffraction experiments at the X-ray Powder the unidentified phase. Clearly the lattice response in
Diffraction (XPD) beamline of the National this temperature range is complex and below the
Synchrotron Light Source-II (NSLS-II) [123]. The high- onset of sintering. Additionally, the large difference in
flux, high-energy, and high-temperature heating cap­ the lattice parameters for the MgO + LiF mixture and
abilities at the XPD beamline [124] effectively facilitate reference MgO persist at elevated temperatures where
capturing the atomic and crystallographic evolution enhanced sintering is observable. A liquid phase sin­
while sintering MgO and shed light on the phase tering mechanism does not appear to be plausible, due
evolution with the lithium bearing salt dopants. to the significant densification at temperatures where
Utilizing the NSLS-II, the time resolved x-ray capabil­ no liquid is observed. We thus confirm our initial spec­
ities (sub second-to-second time scale) of XPD are ulation that the fugitive LiF promotes the formation of
needed to resolve the evolution of the atomic struc­ a crystalline eutectic phase as well as a substantially
ture of the Li-MgO powder mixtures as the specimens high point defect concentration (even in the absence
are cycled through the sintering temperature window of applied pressure), which synergistically act together
(RT- 1100 C). In situ sintering experiments were carried to enhanced sintering and grain growth in MgO.
out with lithium salt doped MgO: 5.0 wt.% LiF +MgO Moreover, it appears clear that the effect of the Li-
mixtures loaded into a custom hexapole lamp furnace bearing salt on sintering is not solely a surface phe­
sintering cell. XRD patterns were measured from RT to nomenon. We plan to pursue this phenomenon with
1100°C. The raw 2D XRD images were reduced 1D XRD future in situ XRD experiments using a wider range of
patterns and analyzed using high-throughput software lithium-salt addition and including a range of the salts
to quantify the evolution of the lattice [125,126]. to isolate the emergent phase. These in situ

Figure 11. (a) In situ XRD patterns for MgO + 5 wt.% LiF powder mixture. (b) Quantitative lattice parameters for the MgO phase as
a function of temperature. Lattice parameter for bulk MgO (with no LiF sintering additive) is given for reference (data are from Ref
[127].).
 JOURNAL OF ASIAN CERAMIC SOCIETIES 27

experiments are appreciably sensitive to the atomic For the case of the Be-metal of (Figure 12 (a)) sinter­
defects and crystallographic phase evolution and ing occurred normally though a limited reaction occurs
shed considerable light on the sintering dynamics in at the matrix-entrainment interface. The Be-metal par­
this technologically relevant material. ticle size utilized was approximately 400 μm with a pur­
ity of >99.9%. During sintering a reaction occurs,
3.4.2. Example MgO-matrix two-phase moderators enhanced by the presence of LiF, whereby Be reduces
In comparison with potential SiC, Al2O3, or MgAl2O4- the MgO to form BeO on the core of the powder with
matrix systems, the MgO-matrix system as describe a limited amount of free Mg forming MgF2, a high
above allows a very wide range of potential entrained melting point (1263°C) tetragonal phase. Depending
phases due to low required sintering pressure (10 MPa on initial Be-metal size a core-shell microstructure
or less) and very low processing temperature (~730– results with the entrainment being a Be-core sur­
1030°C). Referring to temperature capability of the rounded by the BeO reaction product. While this
entrainment materials Table 1 it appears that the phase can be limited through appropriate selection
potential exists for a MgO-matrix composite to incor­ of sintering conditions and is not a neutronic penalty
porate most of the identified materials including Be- as both Mg and F have low neutron absorption cross
metal, the low-temperature ceramic moderators such sections, it may be undesirable given its tetragonal
as Be411C and Be2C, and remarkably, a wide array of structure insofar as composite irradiation stability is
metal hydrides. At this point a number of two-phase concerned. Using BeO as starting powder in place of
moderators have been produced following the generic Be obviously eliminates this reaction, resulting in
MgO sintering recipe outlined in Figure 9 in the highly dense and phase-pure composite (Figure 12
entrainment volume fraction range of 10–40%. Two- (b)), with only a small penalty over the Be-metal com­
dimensional x-ray tomography slices through example posite. Figure 13 provides the DCS sintering curve,
moderating composites are provided in the images thermal conductivity and thermal expansion for this
Figure 12. composite. As expected, the thermal conductivity is

Figure 12. X-Ray tomographic images of four two-phase composite moderators: (a) MgO-40%Be, (b) MgO-40%BeO, (c)
MgO:30%Be2C, and (d) MgO:20%ZrH1.6. All composites fabricated with a 1% LiF additive with a 10 MPa applied pressure, 50°C/
min ramp rate to a flat-top hold of 10 minutes at 1100°C. Sample cooling was carried out at a nominal 50°C/min rate.
28 L. L. SNEAD ET AL.

Figure 13. Sintering curve and thermophysical properties for a MgO-40%BeO composite.

somewhat lower than the rule-of-mixtures (ROM) value The final example composite is provided in 12 (d),
(~180 W/m-K at room temperature,) though agrees being a MgO-ZrH1.6 composite where the hydride
well with the Maxwell model as applied to composite. loading was ~20% of ZrH2 (ε phase), which thermally
Also of note is that as the BeO volume fraction of this decomposes during processing to form the (more irra­
powder is increased from 10 to 40 vol% the composite diation stable δ phase) ZrH1.6. While higher hydride-
relative (to theoretic ROM) density decreases, with loaded composites were fabricated, neutronic analysis
a large intrinsic porosity of the powder itself. In this suggests [128] that compositions near 20% hydride are
case the porosity is an engineered solution to potential optimal for high fuel packing fractions (~0.50) so as not
entrainment strains produced due to helium transmu­ to over-moderate the reactor system. Figure 14 shows
tation or the anisotropic swelling of the BeO. This the calculated initial reactivity for a hydride moderated
engineered porosity can be reduced or eliminated by micro-HTGR. The initial reactivity of a system can pro­
careful selection and treatment of the BeO. As deter­ vided an insight on the optimal core configuration. As
mined by x-ray tomography the matrix MgO phase shown, the hydride moderated system is very sensitive
remains fully dense with an absence of large or inter­ to changes in the volume fraction of the entrained
connected porosity. moderator and fuel packing fraction. A significant pro­
The formation of MgO-Be2C composite, image pro­ cessing difference between the hydride-entrained and
vided in Figure 12 (c) followed the same processing as beryllium-entrained composite is the application of
that of the BeO composite, using Be2C powder fabri­ hydrogen-overpressure during DCS sintering for the
cated through the reaction of nominally 3 μm graphite case of the hydride-entrained composite. Simply, by
powder reacted with beryllium vapor. The resulting providing a partial pressure of hydrogen environment
powder was highly crystalline Be2C of similar size during processing the effective plateau pressure (cf
distribution.

Figure 14. Initial reactivity for a hydride moderated micro-HTGR as a function of fuel packing fraction and entrained moderator
volume percent.
 JOURNAL OF ASIAN CERAMIC SOCIETIES 29

Figure 4) is shifted to the right, effectively increasing at Stony Brook. Nanomaterials, which is a U.S. DOE Office
the allowable processing window for these materi­ of Science Facility, at Brookhaven National Laboratory
als [129]. under Contract No.DE-SC-0012704. This research used
resources at XPD beamline of the National Synchrotron
Light Source II, a U.S. Department of Energy (DOE) Office
of Science User Facility operated for the DOE Office of
4. Concluding remarks Science by Brookhaven National Laboratory under
Contract No. DESC-0012704.
As a result of the work under this US Department of
Energy ARPA-E Meitner grant, a range of new compo­
site materials have envisioned, fabricated, and ana­
Disclosure statement
lyzed for their performance as high-temperature
moderators for nuclear systems. General conclusions No potential conflict of interest was reported by the
regarding the applicability of these systems elevated author(s).
temperature nuclear reactor moderators are as follows:

(1) The simple example of two phase, ceramic Funding

matrix composite based on the MgO matrix This work was supported by the Advanced Research Projects
with highly moderating entrained phase offer Agency - Energy [DE-AR000087]; FP7 Fusion Energy Research
superior neutronic capability to the historic gra­ [DE-SC0018332].
phite they are intended to replace. Potential
enabling attributes of these advanced compo­
site moderators as compared to nuclear gra­ ORCID
phite are potentially decreased core size,
Nick Brown http://orcid.org/0000-0002-0231-7728
decreased uranium loading, less drastic as-
irradiated property changes, and lifetime
components. References
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