Towards Using Calcium

Sulfoaluminate Cements
for Nuclear Waste Immobilisation
Judith Q Zhou1, Neil B Milestone1 and Martin Hayes2
1 Immobilisation

Science Laboratory (ISL), University of Sheffield

2 Nexia Solutions (formerly BNFL/NSTS)
12-13 April 2005, Cambridge University

Outline

Nuclear waste classification

Current cementing processes
Challenges for current formulations
Alternative cement system:
CSA preliminary investigation
Summary

Nuclear Waste Classification

Low level waste (LLW):
4GBq/Te alpha or 12GBq/Te beta gamma

Intermediate level waste (ILW):

Above levels for LLW but are not significantly heat
generating.

High level waste (HLW):

Significantly heat generating

Typical Nuclear Waste Streams

Waste Category
Cladding and dissolver residues

Reactor dismantling components

Slurries
Effluent treatment
Technological
(high beta/gamma, low alpha)
Transuranic (TRU)

Typical Waste Streams

Magnox, aluminium, stainless steel
and zircalloy fuel cladding,
centrifuge cake
Stainless steel debris, graphite
sleeves
Corroded Magnox sludge, fuel pond
sludges
BaCO3 Slurry, flocs, natural ion
exchangers, synthetic zeolites
Filters, solid scrap items,
combustible wastes
Solid scrap, combustible wastes,
flocs, incinerator ash

Challenges for Current Formulations

Composite OPC systems are currently used as a
routine industrial operation in the UK
OPC is replaced by high levels of PFA or BFS
These replacements provide cementing systems
good fluidity
lowered heat of hydration
a matrix with lower porosity and permeability
insolubility of many metal hydroxides and hydrated oxides
high internal pH
available water for longer term corrosion

CSA Cement (I)

Low-energy and environmentally friendly cement
Lower manufacturing temperature, 100 200oC lower than that
of OPC
Soft clinker, ~ 25% saving in energy for grinding may be
achieved
Less CaCO3 needed, lower CO2 emission , ~ 40% reduction is
possible
10 30 % gypsum/anhydrite added
Use waste materials: slag, bottom ash, PFA, pyrite ash etc.

CSA Cement (II)

Main Properties

Rapid strength development and setting

Controlled shrinkage compensation/expansion
Good resistance to sulfate attack and corrosion
Good resistance to freezing, - 10 ~ - 20oC
Low alkalinity, pH 10 ~ 12

Main clinker phases

yeelimite(3CaO.3Al2O3.CaSO4), iron phase(4CaO.Al2O3.Fe2O3),
12CaO.7Al2O3, CaO.Al2O3

Main hydration phases

ettringite 3CaO.Al2O3.3CaSO4.32H2O, Al(OH)3
monosulfate 3CaO.Al2O3.CaSO4.12H2O

Ettringite
Potential for immobilisation
Reported ion substitutions in ettringite structure [1]
Ca2+ site: Sr2+, Ba2+, Pb2+, Cd2+, Co2+, Ni2+, Zn2+
Al3+ site: Cr3+, Si4+, Fe3+, Mn3+, Ni3+, Co3+, Ti3+
SO42- site: B(OH)4-, CO32-, Cl-, OH-, CrO42-, AsO43-, SeO42-, VO43-, BrO3-,
NO3-, MoO42-, ClO3-, SO32-, IO3OH- site: O2-

[1] M.

L. D. Gougar, B. E. Scheetz , D. M. Roy: Ettringite and C-S-H Portland cement phases for
waste ion immobilization: A review, Waste Manag., 16 (1996) 295-303

Experimental
CSA cement :Provided by Lafarge Cement UK (commercial name Rockfast 450)
Mixes

Rockfast/anhydrite (wt%)
65/35
70/30
75/25
80/20

Water/solid ratio
0.75,0.67,0.60
0.75,0.67,0.60
0.75,0.67,0.60
0.75,0.67,0.60
Total 12 mixes

Curing
20oC, 40oC and 60oC for 1, 3, 7 and 28 days at 95% r.h.

Characterisation
Fluidity, pH, temperature, XRD

Corrosion trial of Al
Comparison of Al rod embedded in BFS/OPC=90/10, w/s =0.33 and
Rockfast/anhydrite=75/25, w/s = 0.67 at 60oC

Fluidity
1200

1200

R/A = 65/35

1000

R/A = 75/25

R/A = 75/25
Fludity (mm)

Fludity (mm)

1000

R/A = 65/35

R/A = 70/30

R/A = 70/30

R/A = 80/20

800
600

R/A = 80/20

800
600
400

400

200

200

50

100
150
Time after mixing (min)

200

50

250

100
150
Time after mixing (min)

1200

R/ A=70/ 30, w/ s=0. 67

1000

R/A = 70/30

R/ A=75/ 25, w/ s=0. 67

R/ A=80/ 20, w/ s=0. 67

R/A = 75/25
R/A = 80/20

800
600
400

Fl ui di t y ( mm)

Fludity (mm)

R/ A=65/ 35, w/ s=0. 67

R/A = 65/35

1000

250

w/s = 0.67

w/s = 0.75
1200

200

800

BFS/ OPC=75/ 25, w/ s=0. 35

600
400

200
200

0
0

50

100

150

Time after mixing (min)

200

250

0
0

50

100

150
Ti me ( mi nut es)

w/s = 0.60

200

250

300

Temperature, bleeding and pH

Temperature rising and bleeding at w/s = 0.67
Rockfast/Anhydrite
Bleeding
Wt % ratio
T (oC/2Kg Powder) (ml/100ml grout)

63/35
70/30
75/25
80/20

4.0
7.4
3.4
4.4

pH values: 10.5 ~ 11.5

Setting time: within 24 hours

0.2
0.1
0.2
0.1

XRD Traces (R/A=75/25, w/s=0.67)

E

E: ettringite
G: gehlenite
A: anhydrite
Y: yeelimite

G+A
E

E
E

A
GE

E
E

GE

E
E E

E+A
G+E A
A
E

E
E

E
E A

28 days
G+A

I nt ensi t y

7 days

3 days

1 day

Y
Y

18

28

38
2 Thet a

48

58

Corrosion Trials of Al

BFS/OPC=90/10, w/s = 0.33, 60oC at 1, 7 and 28days

CSA/Anhydrite=75/25, w/s = 0.67, 60oC at 1, 7 and 28days

Summary (I)
Results of the ongoing study indicate that ettringite
based CSA cement offers

good fluidity due to high w/s ratio which can be adjusted by

changing formulation
high w/s ratios cause little bleeding, due to water being
chemically bound and may also not be available for long term
corrosion
low internal pH leads to reduced corrosion of Al, possibly
also due to relatively dry internal environment

Together with the great potential immobilising ability of

ettringite, CSA cement is a promising candidate as an
alternative cement for nuclear waste immobilisation.

Summary (II)
More investigations are needed on

better understanding of corrosion behaviour

temperature control
understanding of incorporation mechanism of
wastes
long term durability
field trial to test practical application on large scale

Acknowledgement
The authors would like to thank Nexia Solutions
UK, for financial support and helpful
discussion within ISL