Something about nuclear graphite

Tongxiang LIANG Nuclear Graphite Research Group Institute of Nuclear and New Energy Technology Tsinghua University txliang@tsinghua.edu.cn

OVERVIEW
History Requirements Manufacturing Microstructure Irradiation performance Disposal of spent graphite

History of nuclear graphite

 In 1919 Rutherford discovered the proton, and put out the idea that there could be a particle with mass but no charge. He called it a neutron. James Chadwick discovered the neutron in 1932, received the Nobel Prize for his discovery in 1935. Neutron is the golden key to open the gate of nuclear energy

 Physicists soon found that the neutron is an ideal "bullet" for bombarding other nuclei. In 1934, Enrico Fermi found that slow (thermal) neutrons striking the target will be more likely to collide with silver atoms; the increased collisions result in higher radioactivity. 1938, Otto Hahn, Lise Meitner and Fritz Strassmann discovered that uranium nuclei split when bombarded with neutrons.

 The nuclear cross section of U235 for slow neutrons is about 1000 barns, while for fast neutrons it is in the order of 1 barn. Therefore thermal neutrons are more likely to cause U235 to fission than to be captured by U238. How to obtain slow neutron? use a neutron moderator such as graphite, Be, water, to slow neutrons until they approach the average kinetic energy of the surrounding particles, that is, to reduce the speed of the neutron.

 In 1942 the Manhattan Engineer Project was set up in the United. Scientists recruited to produce an atom bomb included Robert Oppenheimer (USA), David Bohm (USA), Leo
Szilard (Hungary), Eugene Wigner (Hungary), Rudolf Peierls (Germany), Otto Frisch (Germany), Niels Bohr (Denmark), Felix Bloch (Switzerland), James Franck (Germany), James Chadwick (Britain), Emilio Segre (Italy), Enrico Fermi (Italy), Klaus Fuchs (Germany) and Edward Teller (Hungary). In order to produce Pu, Chicago Pile 1 (CP-1) reactor was built.

CP-1 reactor was a pile of uranium and graphite blocks, graphite is neutron moderator

Fuel of CP1

Graphite from CP 1

Then, graphite has been widely used as a moderator, reflector and fuel matrix in various types of nuclear reactors, such as gas cooled reactor (e.g. AGR, MAGNOX), Russian RBMK reactors, high temperature gas cooled reactor (Dragon, Peach Bottom, AVR, THTR-300, Fort St. Vain, HTTR, HTR-10 ) and so on.

Magnox

AVR

THTR 300

Dragon reactor

M.S.T. Price, Nucl Eng and Design, 251 (2012) 60-68

HTR-10

Requirements

Nuclear designer requires:

six high and four low

High purity (neutronic and waste point of view, Boron content) High density (The greater the density, the greater its moderation of neutron flux) High irradiation stability (The irradiation behavior is strongly influenced by the source of the pitch, the coke and the manufacturing process) High thermal conductivity High strength High oxidation resistivity

 low anisotropy, less than 1.1, defined by coefficient of thermal expansion (CTE) in orthogonal directions low CTE, ~4 x 10-6 K-1 (20 - 120) low elastic modulus low cost
The graphite crystal is anisotropic; i.e. its properties are different in perpendicular and parallel directions relative to the principal alignment of the basic planes

Basic properties of nuclear graphite

Nuclear graphite Filler Mean particle size ( m) process Density (g/cm3) Flexural strength (N/mm2) Tensile strength (N/mm2) Compressive strength (N/mm2) Thermal conductivity (W/mK) CTE (10-6/) Anisotropy IG11 petroleum coke 20 isostatic pressing 1.78 37 25 77 78 4.1 1.05 1.03 NBG18 Pitch coke 300 vibration molding 1.85 30 24 77

Philippe Beghein et al, Nuclear Eng and Design, 251 (2012) 146-149

Philippe Beghein et al, Nuclear Eng and Design, 251 (2012) 146-149

Nuclear Graphite Manufacturing

 cold isostatic pressing or vibration molding is used for shaping in order to get low anisotropy. After baking (carbonization), the artifact is typically impregnated with a petroleum pitch and re-baked to get densification. Impregnation and re-bake may perform several times to attain the required density. Graphitization typically occurs at temperature >2,500C. Additional halogen purification may be required.
W Winders, et al, Project 23747, Graphite Technology Development Plan, PLN-2497. Idaho Falls: Idaho National Lab.2007

Raw materials:
1) Calcined coke-----petroleum or pitch coke (size and distribution) 2) Binder----coal tar pitch (soft point and carbon yield, thermoplastic) 3) impregnants---coal tar pitch or polymer 4) additives

mixing

How to get isotropic graphite?-----coke/manufacture process

A needle coke known as AGOT graphite was used in the Hanford piles and achieved some undesirable results. Needle coke is anisotropic, and when irradiation it develops large internal stresses in one direction, which results in cracking and a decreased irradiation lifetime. Magnox, windscale, WAGR piles used needle coke and extrusion processed graphite as moderator

 Gilsonite coke from natural mine in Utah USA, particles have onion skin structure, molding process gives isotropic property.
Isotropic cokes are favored for nuclear graphite

AGR, THTR 300 used, no longer exist

Needle coke

 Germany developed a second coke method: coke + binder----blended----baked----milled, mix with binder----blended----baked--impregnated----graphitized In order to get isotropic behavior, Isostatic pressing or Vibration molding is used

Isostatically presser

oil

Vibration molding machine

Baking or carbonization 1000~1250, Binder to carbon

A N Jones and B J Marsden, CARBOWASTE Abbeye St Jacut 25th -28th Oct 2010

Using low soft point, high carbon yield pitch

Autoclave Impregnation By pitch to improve density

A N Jones and B J Marsden, CARBOWASTE Abbeye St Jacut 25th -28th Oct 2010

Acheson and lengthwise graphitization furnace

Acheson

lengthwise

Acheson and LWG

semi-products themselves act as resistor

Philippe Beghein et al, Nuclear Eng and Design, 251 (2012) 146-149

The final product

machining

 There is a big shrink rate difference between pitch and coke particles during the baking period, as a result internal stress will be produced that may lead to the cracking of graphite products. The green cokes or mesocarbon microbead (MCMB) surface is chemically active, which makes it easy to combine with binder. Furthermore, coke and binder have a same shrink rate during the heat treatment process. Graphol series graphite designed by Oak Ridge National Laboratory belong to green coke graphite, the damage strain of graphol graphite is larger than that of conventional graphite.

Coke size:
Particle size, pore or crack size and distribution have great effect on the performance of graphite. Isostatic pressing graphite (e.g. IG110) used fine-particle-coke, about 20 m, vibration forming graphite (e.g. NBG18) has a large particle size, 300 m, and they have different fracture behavior. For coarse-particle graphite, it did not break immediately when the crack grow to the critical value. But the fine-particle graphite damaged quickly as the crack began to grow. The fracture toughness is increased due to energy dissipating mechanisms such as crack deflection, crack bridging and pull out. Coarse-particle graphite exhibits low sensitivity on the crack than the fine-particle graphite. Upon repeatedly loading, coarse graphite fracture toughness increased but fine-particle graphite decreased.

Microstructure

J. Kane, et al, Boise State University

Very complex structure

C Karthik, et al, Boise State University

G: Giloscarbon filler particle C: calcination cracks

needle coke filler particle

B: binder phase E: gas entrapment pores

Optical micrograph of two graphite

Paul J Hacker, J. Phys. D: Appl. Phys. 33 (2000) 991998

TEM of Virgin Graphite

Mrozowski cracks, with lengths from tens of nanometres to more than 10 m and width from several nanometres to about 200 nm.

Mrozowski cracks

Upon heating, graphite increases its order of crystallinity

Mrozowski cracks were formed due to the thermal expansion coefficient difference along and normal to the grain of graphite during slow cooling process of graphitisation.

(a) Graphite lattice; (b) turbostratic graphite

Irradiation performance

 Under irradiation, graphite undergo changes in its thermomechanical properties, especially via swelling and irradiationinduced creep, which affects the graphites in-service life time. understanding of these life-limiting phenomena is very important for the development of new nuclear graphite. The current understanding is that the ballistic displacement of carbon atoms caused by irradiation results in the accumulation of interstitial atoms between the basal planes. These interstitial clusters eventually rearrange to form new basal planes resulting in the expansion along the c-axis; however, this explanation has been disputed by several researchers.

The historic nuclear graphite no longer exist; must characterize the microstructures of new nuclear graphite and demonstrate that they exhibit acceptable properties in both the non-irradiated and irradiated state.

Upon neutron irradiation a neutron will knock carbon atoms from the basal plane and cause the formation of a vacancy
New plane forms, c-axis expansion

Irradiation : the <a>-axis shrinkage and <c>-axis growth

The in-plane c-c bond is very strong, the interplanar bonding is weak
Atom is difficult insert into the basal plane

B.T. Kelly et al, IAEA-TECDOC-1154, 2000

46

C. Karthik, et al, Boise State University

the cracks tend to close upon heating

closure of the cracks by electron irradiation

Keyun Wen, et al, Journal of Nuclear Materials 381 (2008) 199203

In-situ e-Beam Irradiation Effects of NBG 18 graphite Crack closing by the swelling of c direction

J. Kane, et al, Boise State University

(1)

(2)

Mrozowksi cracks

In-situ HRTEM of NBG-18 graphite under e-Beam irradiation

J. Kane, et al, Boise State University (3)

At the beginning of irradiation, a-axis shrinking and c-axis swelling, but the swelling is taken up by the accommodation cracks.
Neutron dose

The dimensional change is shrink

After the cracks closed, the c-axis accommodation has been filled, turnaround

swell

Dimensional instability under irradiation is one of the main problems for nuclear graphite

How to determine the lifetime of reflector graphite? Shrinkswell, at the point of 0 changes Lifetime
dimensional variations

low anisotropy has a longer lifetime

Turnaround. After turnaround pore generation and expansion will continue until internal stresses are large enough to propagate cracks Neutron dose
53

For the moderator and reflector of HTGR, the lifetime of graphite is about 40 years, it must have a higher irradiation stability. The irradiation behavior is strongly influenced by its crystallographic structure, i.e., by the source of the pitch, the coke and the manufacturing process. Which kind of raw materials and process is benefit for irradiation? Unknown! need further research.

Other behavior
Graphite crystal
has strong bonds in the basal plane, a-axis; weak bonds in c direction Modulus is greater in a direction

Polycrystalline graphite Always have some degree of preferred orientation,--with grain (WG) or against grain (AG)

Irradiation
Irradiation defects pinning dislocation, and crack closure, so modulus increase; high dose, large pores and crack, modulus decrease
Cracks closure lead to the CTE rise

Higher modulus in WG direction

The coefficient of thermal expansion is much greater in c direction

Lower CTE in WG direction

Heat is transferred by lattice vibration (phonon) along the basal plane, thermal conductivity is greater in a direction

Higher thermal conductivity in WG direction

Irradiation induce defects, phonon-phonon scattering, thermal conductivity decrease

Irr. dose

200peak as the irradiation dose (at 30 ), irradiation reduce the graphitization degree
56

Change in Youngs modulus

1.4 1.2 1 CTE /0 0.8 0.6

940oC 430oC 600oC 1240oC

0.4

0.2
0 0 100 Dose n/cm2 EDND x 102 200

Just like Youngs modulus, Initial increase of CTE attributed to closure of Mrozowski cracks. Subsequent decrease attributed to opening of new porosity.

Thermal conductivity decreases as the neutron dose increasing

59

Disposal of spent graphite

After decommissioning, a HTGR with 200MW will produce about 600 tons radioactive nuclear graphite, and during the annual operation, the discharged spent fuel contains about 60 tons graphite. Up till now about 250,000 tons irradiated graphite has to be disposed as radioactive waste, though with low radioactivity. How to dispose the large volume of contaminated graphite reasonably needs to be addressed if we want to develop HTGR reactor sustainably.
Low Level Waste (LLW).

 Most radioisotopes can be removed by high temperature annealing. 14C has a half-life of 5730 years, and is a biologically hazardous substance because of its readily assimilation by the human body, how to dispose 14C becomes the key issue for management of nuclear graphite during decommissioning of graphite moderated reactors.

J. Fachinger et alNuclear Engineering and Design 238 (2008) 3086

Experimentally determined 14C specific activity was 13020 kBq/g for the RBMK-1500 reactor

14C

activity measured by LSC as a function of fast neutron fluence. (D. Lexa, J of Nuclear Materials 2006,348,122)--the ASTRA research reactor

There are several principal solutions possible: Packing and disposal of graphite in appropriate repositories Incineration of graphite with the exhaust of CO2 gas Recycling. is the most challenging option Every management route has its strong and weak aspects.
Disposal option is simple and cheap, but this requires building specialized repositories. Disposal is not very attractive from the point of view of nuclear energy sustainability. Incineration means that all 14C would be emitted to the atmosphere. Incineration of one RBMK-1500 reactor graphite (1700 tons of graphite, 71014 Bq of 14C)would increase the amount of 14C in the atmosphere by 0.6%.

 Recycling of nuclear graphite is of great practical value. However, it is very difficult to separate 14C from the graphite matrix. Steam pyrolysis is an effective technology for the remove of 14C The mechanism of steam pyrolysis for removing 14C is based on the fact: most of 14C is located on the graphite surface, the inner surface of pores or grain boundary, then it becomes 14CO2 and 14C O when oxidized by water or oxygen.
14 N + n ----14C

Schematic drawing of steam pyrolysis

Summary
HTGR graphites life is about 40 years, if prolong to 60 years, much more research works should be done on graphite. Research should focus on the following materials: Graphite using green coke as raw material has a high fracture strain, vibration molding of coarse particle graphite shows special fracture toughness. In recent decades, materials science has made great progress, but nuclear graphite research came to a standstill since the 1980s. Improvement on performances of nuclear graphite may be inspired by introducing new ideas, including nano-carbon materials, antioxidation coating, mesophase carbon, and so on. Steam pyrolysis method is the effective technology for removing 14C from spent graphite. Recycling of waste graphite for nuclear graphite fabrication is of great practical value due to sustainability.

Nuclear graphite research institutions

The University of Manchester University of Bath Oak Ridge National Laboratory University of Oxford SGL INET---will publish some papers in three years

INETs plan
Research program in my group: Manufacture and properties of nuclear graphite Irradiation of graphite, including modeling and simulation by the first principle, Molecular Dynamics, MC.. Disposal of nuclear graphite waste