asbestos case studies 1: water pipes made of asbestos...
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Asbestos case studies 1:Water pipes made of asbestos cement
Erzsébet Tóth (Eötvös L. University, Budapest)
31. 08. 2007
Asbestos-cement water pipe production: Selyp (Hungary, 2000)
Final products
Raw material: chrysotileasbestos from Canada
Production waste
Fibre-cement production: Technology is more or less independent of the fibre type used: asbestos is now replaced by cellulose and synthetic fibres.
After forming the pipe/roofing tile/corrugated sheet etc., the product is kept for a while in warm and steamy environment to enhance the fastening and hydration of the cement.
Fibre-cement production: binding of the cement
Slurry is made up of fibers, portland cement and water
discussed next 60–90%wet process
Concrete - cement Definitions
‘ Cement is a hydraulic binder, i.e. a finely ground inorganic material which, when mixed with water, forms a paste which sets and hardens by means of hydration reactions and processes and which after hardening, retains its strenght and stability even under water ’ ENV 197-1: CEM cement
‘ Portland cement is a hydraulic cement produced by pulverizing portland-cement clinker ‘ ASTM C 219-94
‘ Concrete is a composite material produced by using cement to bind fine and coarse aggregate (sand and gravel) into a dense coherent mass’.
Mortar: use of only fine aggregates (sand)
Jan Elsen, EMU School and ERASMUS IP on Technical Mineralogy, 2006
Ettringite
Alite
Cement chemical nomenclature
Jan Elsen, EMU School and ERASMUS IP on Technical Mineralogy, 2006
Cement mineralogy
The microscopical study of Portland cement clinker to determine the mineralogy started at the end of the 19th century.
Törnebohm gave the names alite, belite, celite and felite to four distinctive crystalline components + isotropic residue.
Later:
•Alite = tricalcium silicate C3S
•Belite and felite = dicalcium silicate C2S
•Celite = Calcium Alumino Ferrite – mainly C4AF
•Isotropic residue = Calcium Aluminates – mainly C3A
Jan Elsen, EMU School and ERASMUS IP on Technical Mineralogy, 2006
Cement mineralogy
Actually Portland cement contains four major mineral phases:
•Alite = tricalcium silicate C3S 50-70 %
•Belite = dicalcium silicate C2S 15-30 %
•Aluminate phase = mainly tricalcium aluminate C3A 5-10%
•Ferrite phase = mainly C4AF 5-15 %
(brownmillerite)
For asbestos (and fiber) cement: high C3S and low C3A is the best
Jan Elsen, EMU School and ERASMUS IP on Technical Mineralogy, 2006
Jan Elsen, EMU School and ERASMUS IP on Technical Mineralogy, 2006
Cement mineralogy - Alite – C3S
- Orthosilicate – monoclinic (M1 or M3)
- Biaxial Negative with 2V ~ 20-60°
- Low birefringence 0.002-0.010 ~ first order gray int. Color
- colourless with // polars – high positive relief
- 3 triclinic - 3 monoclinic and 1 rhombohedral polymorphs exist
- First crystal structure determination by Jeffery (1952)
Jan Elsen, EMU School and ERASMUS IP on Technical Mineralogy, 2006
Alite - Mineral formula: Ca3SiO5- Chemical formula: 3CaO.SiO2 (C3S)
Jan Elsen, EMU School and ERASMUS IP on Technical Mineralogy, 2006
Alite – crossed polarsJan Elsen, EMU School and ERASMUS IP on Technical Mineralogy, 2006
Cement mineralogy - Belite
Larnite Ca2SiO3 is the natural analogue of belite
- Five polymorps exist at ordinary pressures the β – C2S polymorph is most common.
- Monoclinic - Space group P21/n
- Biaxial Negative with 2V ~ 64-69°
- second order interference colors
- colourless – (amber) yellow with // polars – high positive relief
- First cristal structure determination by Midgley (1952)
Jan Elsen, EMU School and ERASMUS IP on Technical Mineralogy, 2006
- Mineral formula: Ca2SiO4- Chemical fomula: 2CaO.SiO2 (C2S)Belite
Jan Elsen, EMU School and ERASMUS IP on Technical Mineralogy, 2006
Belite- crossed polars
Jan Elsen, EMU School and ERASMUS IP on Technical Mineralogy, 2006
Cement mineralogy - Aluminate Phase
- Cubic
- Typically fills interstices between crystals of belite and ferrite.
- light-brown color
Cement mineralogy - ferrite phase
- Orthorombic – biaxial negative - Composition ranges from C5A2F to C6AF2
- Typically fills interstices between crystals.
- light-brown – yellow color
- brownmillerite is a rare natural analogue.
Jan Elsen, EMU School and ERASMUS IP on Technical Mineralogy, 2006
Hydration of cement minerals
Belite + water
C2S + 2H CSH + CH
Ca(OH)2 ; Portlandite
Calcium Silicate Hydrate
Jan Elsen, EMU School and ERASMUS IP on Technical Mineralogy, 2006
Cement mineralogy - portlandite Ca(OH)2
– Hexagonal - Uniaxial Negative
- first-order red and second –order blue int. colors
- colourless , forming minute hexagonal plates
- Crystal structure is identical to the Mg(OH)2 structure
Layered structure – with Ca octahedrally and O tetrahedrally coordinated. Interlayers forces are weak giving good (0001) cleavage ; P-3m1 spage group
Jan Elsen, EMU School and ERASMUS IP on Technical Mineralogy, 2006
Portlandite - Ca(OH)2
Jan Elsen, EMU School and ERASMUS IP on Technical Mineralogy, 2006
CSH - Calcium Silicate Hydrate
SEM - BSE image Jan Elsen, EMU School and ERASMUS IP on Technical Mineralogy, 2006
Fundamental details about the most important cement hydrates, the calcium silicate hydrates or CSH-phases (structure, hydration kinetics, bonding mechanism etc.) are still unknown. This is due to their small particle size (~20 nm), low ordering, heterogeneity and low stability.
-Merlino S, Bonacorssi E, Armbruster T Am Mineral., 1999, 84:1613–1621
-Merlino S, Bonaccorsi E, Armbruster T Eur J Mineral., 2001, 13 :577-590
-E. Bonaccorsi, S. Merlino, H. F. W. Taylor, Cem. Conc. Res., 2004, 34, 1481.
Tobermorite1.4 nm
80-100°C
Tobermorite1.1 nm
300°C
Tobermorite0.9 nm
Occurs as a natural mineral
Jan Elsen, EMU School and ERASMUS IP on Technical Mineralogy, 2006
hydrated Alite GrainJan Elsen, EMU School and ERASMUS IP on Technical Mineralogy, 2006
Asbestos cement water pipes –following decades of use
VT: water-pipe (17th district Budapest, age unknown)
VR: water-pipe operating for 44 years (1028 Budapest, between 1956–2000)
Strong internal alteration: stronger interaction with potable water than with soil humidity
potable water is typically hard water in the region
CarbonationConcrete will carbonate if CO2 from air or from water enters the concrete according to:
- Ca(OH)2 + CO2 --> CaCO3 + H2O
- Calcium Silicate hydrates + CO2 -> various intermediate mineral phases
Various intermediate mineral phases -> CaCO3 + H2O + SiO2.nH2O
- Ferrite hydrates + CO2 --> CaCO3 + hydrated alumina + iron oxides
The carbonation process requires the presence of water because CO2 dissolves in water forming H2CO3. -If the concrete is too dry (RH <40%) CO2 cannot dissolve and no carbonation occurs. - If the concrete is too wet (RH >90%) CO2 cannot enter the concrete and the concrete will not carbonate. Optimal conditions for carbonation occur at a RH of 50% (range 40-90%).
Jan Elsen, EMU School and ERASMUS IP on Technical Mineralogy, 2006
CarbonationConcrete surface
Carbonated zone
Jan Elsen, EMU School and ERASMUS IP on Technical Mineralogy, 2006
Carbonation combined with leaching
Natural water can leach carbonates, formation of soluble calcium bicarbonate, the only remaining product is a gelatinous silica product.
Diagram illustrating the zones of soft water attack (St John et al. 1998)
Jan Elsen, EMU School and ERASMUS IP on Technical Mineralogy, 2006
Free asbestos web on the inner surface of the water pipe, in direct contact with the potable water
Mg, Si, O – serpentine asbestos
Ca – cement material
VR red alteration zone, thin section
Mg, Si, O – serpentine asbestos
Ca – cement material
VR red alteration zone, thin section
XPD of the VR water pipe
B: brownmillerite; C: calcite; CHR: chrysotile; G: gypsum; K: kaolinite; L: larnite; P: portlandite; Q: quartz; V: vaterite; 10Å: TOT layer silicatered rectangle indicates the region of the main clinker phases
Strong internal alteration: stronger interaction with potable water than with soil humidity
potable water is typically hard water in the region
XPD of the VR water pipe
B: brownmillerite; C: calcite; CHR: chrysotile; G: gypsum; K: kaolinite; L: larnite; P: portlandite; Q: quartz; V: vaterite; 10Å: TOT layer silicatered rectangle indicates the region of main clinker phases
Alteration zonation in water pipes1. Free web of asbestos fibres (thickness: 1–2 mm) with a dark
brown crust (thickness ~0.1 mm)Crust composition: Fe-Mn-(oxy)-hydroxides (inferred from dark brown colour), quartz, calcite, gypsum, organic material(?)
2. Red alteration zone (thickness: 1–2 mm)Composition: vaterite, calcite, chrysotile, (quartz)
3. Pale grey alteration zone (thickness: 3 mm)Composition: calcite, vaterite, brownmillerite, chrysotile
4. Dark grey (unaltered) zone (thickness: 6–10 mm)Composition: portlandite, brownmillerite, larnite (tricalcium-silicate?, mayenite?), chrysotile
5. Yellow outer mineral crust (thickness: 1 mm)Composition: calcite, gypsum, quartz, kaolinite?, 10Å-layer silicate
Conclusions1. Asbestos cement water pipes are corrobated both by drinking water
(inside) and soil humidity (outside). The inside interaction is much more pronounced than the outside one.
2. Interaction with drinking water: cement material (and partly also serpentine asbestos) is replaced by CaCO3 polymorphs, calcite and vaterite. Alteration zonation develops outwards.
3. As a consequence of cement consumption, a free web of asbestos fibers develops on the inner surface of the pipe, which is a potential contaminant of drinking water. The associated health risk has to be assessed in the future (water pipes laid down in the 1960-1980-ies may serve till 2020-2030!!!!!).
4. Interaction with soil humidity (outer pipe surface): cement is only a little bit attacked, and a protective mineral layer – made of calcite and gypsum – develops on the outer surface of the pipe. No real alteration zonation inwards.
5. The observed effects will be the same for other fibre-cement pipes as well, therefore the replacing fibres need to be tested for their possible health effects.