The present invention relates to the manufacture of ceramic articles
and, particularly but not exclusively, to the manufacture of ceramic pellets such
as nuclear fuel pellets.
In general, when a particulate material is compacted in a die, particle-particle
friction and die-wall-particle friction result in variations in the applied pressure
in the particulate body and, in consequence, the compacted body has a non-uniform
pressed density. The non-uniform pressed density of the compact gives rise to a
differential shrinkage during subsequent sintering, resulting in distortion of the
ceramic article. Even when sintering is not accompanied by shrinkage, the nonuniformity
of density remains in the sintered component and is a source of weakness.
Nuclear fuel pellets are ceramic substantially cylindrical solid or
hollow bodies which are composed mainly or wholly of an oxide of uranium, especially
UO2. Collections of such pellets are used together in a sheath providing
a fuel rod or pin. Assemblies of such rods or pins are employed as the active elements
in a nuclear reactor.
In a conventional process for the manufacture of nuclear fuel pellets,
a uranic oxide powder, eg manufactured in the manner described in EP 0277708, is
compacted or compressed in a die or mould and then sintered usually over a period
of several hours at least, usually in a reducing atmosphere at elevated temperatures,
eg 1500°C to 1800°C.
Document US-A-3 823 067 discloses a method of manufacturing a ceramic
article including the steps of forming a body of particulate material, compressing
the body at its ends and sintering the body wherein the body is formed prior to
compression of discrete layers of particulate material having different bulk particles
It is desirable for the pellets to be produced with a body shape which
is a right circular cylinder. Product specifications normally require such a shape.
However, pellets produced in the conventional manner described above may not, after
sintering, be obtained with a right circular cylindrical shape even though the cavity
of the die or mould used to form the pellet shape is itself a perfect right circular
cylinder. The pellets are often produced with a shape which has a body waist in
a wheatsheaf-like profile, ie the cross-sectional area (perpendicular to the pellet
axis) taken at different points along the length of the pellet is less near the
middle of the pellet than near the ends of the pellet. Grinding of the pellets is
normally required after sintering to meet product specifications. Such grinding
is both time consuming and costly.
The purpose of the present invention is to reduce or eliminate the
need for such grinding following sintering.
According to the present invention there is provided a method of manufacturing
a ceramic article as disclosed in claim 1.
The ceramic article may comprise a ceramic pellet having a substantially
The ceramic pellet may comprise a nuclear fuel pellet and the particulate
material may comprise nuclear fuel material.
We have found by experimental analysis that the wheatsheaf shaped
profile obtained in the prior art is caused by sintering a green pellet having a
density which is less in its interior region than at its ends. This differential
density profile is caused in the following way. In the usual method of pressing
a green pellet from a powder, the powder is introduced into a right circular cylindrical
die cavity and the powder is compressed at its ends. Owing to friction effects within
the powder body, there is a variation in load experienced by different regions within
the body and a slight barrelling of the pellet body occurs near the middle of the
pellet. The barrelled region has a lower density than the end regions of the body
because the same particles occupy a greater volume.
By employing regions of particulate material having different densities
prior to compaction in accordance with the present invention the reduction in density
caused upon compaction by the aforementioned barrelling effect is compensated for
and a compact having a more uniform density distribution is obtained. This in turn
provides, upon sintering, a sintered pellet having a more uniform cross-sectional
In the method according to the present invention the body of particulate
material may be formed by introducing powder or particles of the nuclear fuel material
into a mould or die cavity having a substantially right circular cylindrical shape.
The said body may prior to compaction comprise discrete layers having
different densities. Such layers may have interfaces which are substantially planar,
eg in a plane orthogonal to the axis of the body. Alternatively, the layer interfaces
may be non-planar eg convex or concave to provide a suitable density profile.
Alternatively, the density change in the said body prior to compaction
may take place gradually, eg linearly with distance, over a portion of the length
of the body.
The said body prior to compaction desirably includes regions at the
ends of the body which have a density less than that in the interior region ie near
the middle of the body.
The different densities in the said body may be achieved by the introduction
of particulate material into a die or mould cavity from a plurality of sources containing
different particulate materials providing different bulk densities, the release
of material from the two sources being controlled so as to give the required density
profile in the body. The different particulate materials may comprise for example
materials of the same composition but which have been treated differently or which
have different particle morphology. The different particle types may comprise, for
example, (a) particles produced from a single powder but pre-compacted using different
pressures to form different density granules, or (b) particles of the same powder
which have on the one hand been milled and on the other hand have not been milled
or (c) particles which on the one hand have a plate-like morphology and on the other
hand, have a sphere-like morphology or (d) combinations of these different types.
Where granulation is employed to produce different density granules
various known granulation methods may be used for the production of granules one
or more of the different density types. For example, pre-compaction in a die followed
by breaking through a sieve may be employed. Alternatively, roll compaction may
The body of particulate material, eg produced in one of the ways described,
may comprise uranium dioxide which may contain optional additives, eg niobia or
gadolinia, or plutonium dioxide (eg up to 6 per cent by weight) to provide a mixed
oxide (MOX) fuel pellet. The particles may also be coated with a small quantity,
eg less than 1 per cent by weight, of a solid lubricant such as zinc stearate which
has been employed in a pre-treatment process or is used in the compaction step,
to treat the powders from which the body is formed (directly or indirectly as pre-compacted
The pre-compaction and sintering steps in the method according to
the present invention may be carried out in a manner similar to that employed in
the prior art although the pressure in the compaction step may be increased with
time gradually to a maximum, eg 6-7 tonnes per cm2.
The maximum compaction pressure may be from 1 to 10 Te/cm2.
The sintering step may be carried out as in the prior art in an inert gas atmosphere
or in a reducing atmosphere, eg hydrogen or a mixture of hydrogen and an inert gas
containing up to ∼99% per cent by weight of hydrogen. The sintering step may
be carried out for at least one preferably several hours, eg >5 hours, at a temperature
in the range 1500°C to 1800°C. A pressure of greater than one atmosphere is desirably
applied during the sintering step.
The present invention beneficially and unexpectedly allows ceramic,
eg nuclear fuel, pellets to be produced which in profile have sides which are more
straight than those obtained immediately after sintering in the prior art. The need
for costly post-sinter grinding is thereby reduced or eliminated.
Although the present invention is primarily intended for the production
of ceramic, eg nuclear fuel, pellets which in axial cross-section are straight sided
pellets having grooves in their curved surfaces or barrel-shaped pellets required
for particular applications may also be produced using the invention.
The pellets produced by the present invention may be substantially
all solid. Alternatively the pellets may include an axial hole therethrough. The
ends of the pellet may be flat or curved, eg convex. The exact shape of the pellet
will be as usually specified for the particular type of nuclear reactor (eg AGR
or LWR) in which such pellets are to be used in assemblies of fuel rods or pins.
Embodiments of the present invention will now be described by way
of example with reference to the accompanying drawings, in which:
- Figure 1 is a schematic profile of a green (pre-sintered) pellet produced as
in the prior art.
- Figure 2 is a schematic profile of a sintered pellet produced as in the prior
- Figure 3 is a schematic profile of a pellet produced by the method of the present
- Figures 4 and 5 are plots which are actual measured profiles of pellets made
respectively as in the prior art and by the invention.
As shown in Figure 1, a pellet profile having a barrel shape 1 is
produced by compressing a homogenous UO2 or UO2-based powder
in a die or mould cavity of right circular cylindrical cross-section in the conventional
manner described above. Upon sintering of the compressed pellet, a pellet of wheatsheaf-like
shape 2 is formed as shown in Figure 2. The diameter at the waist of the shape 2
may for example by typically 50 µm (ie 25 µm at each side) less than that at the
ends of the pellet for a pellet having dimensions of about 6mm (diameter) by 10mm
Figure 3 shows a pellet profile as obtained by using the method of
the present invention. A right circular cylindrical pellet body shape 3 is formed
by compressing a UO2 or UO2-based powder having three regions
5, 6, 7. In regions 5 and 7 at the ends of the pellet body the density of particles
is d1 and in the region 6 at the middle of the pellet body the density
is d2. The density d2 may be three times greater than d1
for regions 5, 6 and 7 of equal depth when the compaction pressure is 2 tonnes/cm2.
When the pellet shown in Figure 3 is sintered in a conventional way,
eg as described in the following example, a sintered pellet profile substantially
the same as the shape 3 is obtained.
The following illustrative example demonstrates the benefit of the
invention as compared with the prior art.
Ceramic grade uranium dioxide powder manufactured by the Applicants
was used in the experiments. Two types of granules, Type A and Type B, were prepared
from the same UO2 powder as follows.
Type A: Powder was poured into a steel die of diameter 2.54cm and
pressed at a pressure of 0.25 tonnes cm-2 to form a disc shaped powder
compact of thickness approximately 1 cm. The compact was then broken through a #
14 mesh sieve with orifice size 1.2 mm to produce granules. The resultant granules
were placed in a glass jar and 0.2 wt % zinc stearate added. The zinc stearate acts
as a lubricant during die pressing. The jar was then placed on rollers and tumbled
for 10 minutes to improve granule flowability and mix in the stearate.
Type B: These granules were prepared in exactly the same manner as
Type A except that they were pressed at 0.75 tonnes cm-2.
The granules were then pelleted as follows:
Experiment 1 (prior art): 8g of granules of Type B were poured
into a right cylindrical die cavity with diameter 11 mm and then pressed with a
pressure of 2 tonnes cm-2. The resulting compact was then fired under
the following conditions: heating rate 5 C/min ramp rate to 300 C and then a 20
C/min ramp rate up to 1750 C, held at 1750 C for 5 hours and then cooled at 20 C/min.
The atmosphere used was pure hydrogen with 0.5 volume % carbon dioxide at a flow
rate through the furnace of 10 1/min. No pressure was applied during firing. The
fired pellet side profile was then measured on a stylus profile measuring device.
The result of profiling is shown in Figure 4 which clearly shows the previously
described 'wheatsheaf' effect. In Figure 4, the vertical axis represents pellet
radius variation from an arbitrary datum value, as profiled on one side of the pellet
and the horizontal axis represents pellet length in distance from an arbitrary point,
as measured along the same side of the pellet.
Experiment 2 (invention): 3g of granules of Type A were first
placed in the die cavity and the die lightly tapped to ensure the granules lay level.
2g of granules of Type B were placed on top of the Type A granules and again the
die tapped. Finally 3g of granules of Type A were laid on top of the Type B layer.
The granules were then pressed, fired and measured as in Experiment 1 above. The
resultant fired pellet profile shown in Figure 5 is much improved in comparison
to the profile obtained by the prior art procedures as illustrated in Figure 4.
As in Figure 5, the vertical axis represents pellet radius variation and the horizontal
axis represents distance along the pellet both as profiled along the side of the