Calcium Silicate Hydrate

in Fiber Cement Sheets and

Autoclaved Aerated Concrete (AAC)

AUTHOR: WEHRHAHN
Muehlenstrasse 15
Torsten Dietz P.O. Box 18 55
Vice-President WEHRHAHN Group 27738 Delmenhorst/Germany
Delmenhorst, Germany
Phone: ++49-4221-12 71 0
Dr. Klaus Bohnemann Fax: ++49-4221-12 71 80
President WEHRHAHN Group e-mail: [email protected]
Delmenhorst, Germany internet: www.wehrhahn.de

Paper presented at the

—
7th International
Inorganic-Bonded Wood & Fiber Composite Materials Conference

organized by the University of Idaho, Moscow

September 25 - 27, 2000

Sun Valley, Idaho, USA

LIST OF CONTENT

I. Abstract III. What are the main differences

between autoclaving and air
II. Economical production processes curing?
for Fiber Cement, Calcium Silicate
Boards and Autoclaved Aerated III.1 Raw Materials
Concrete (AAC)
III.2 The chemistry of air curing and
high pressure steam curing
II.1 Fiber Cement Sheets/Boards
III.2.1 Air Curing
II.1.1 Production Process
III.2.2 High Pressure Steam Curing
II.2 Calcium Silicate Boards
II.2.1 Production Process IV. Conclusion

II.3 Autoclaved Aerated Concrete (AAC) Literature

II.3.1 Production Process
 Calcium Silicate Hydrate in Fiber Cement Sheets
and Autoclaved Aerated Concrete (AAC)

I. Abstract The presentation introduces the most common

production processes for calcium silicate bonded
Calcium silicate hydrate (C-S-H) is formed on building materials. Answers are given which form
paste hydration of the C3S and C2S phase in of Calcium silicate hydrate is favorable in which
cement already at ordinary temperatures. The building material.
formed C-S-H is of amorphous or poorly
crystalline form.
II. Economical production processes for
High pressure steam curing adds remarkable Fiber Cement, Calcium Silicate Boards and
features in comparison to the cement hydration at Autoclaved Aerated Concrete (AAC) – an
lower temperatures. During autoclaving some overview -
crystallized calcium silicate hydrates are formed.
The crystal structure provides various building Calcium silicate hydrate can be produced either
materials with highly preferred properties such by air curing, e.g. like in cement or concrete, or
as: hydrothermally by high pressure steam curing in
- high strength an autoclave. The production processes for fiber
- dimensional stability (shrink and creep) cement, calcium silicate boards and AAC cover
- higher resistance to chemical attack the whole range from poorly crystallized, semi
crystallized to well crystallized calcium silicate
The crystallized forms of calcium silicate hydrate hydrates.
can for example be found in the following building The type of curing and consequently the type of
materials: calcium silicate hydrate produced has significant
- Fiber Cement Sheets/Boards influences on the properties of the building
- Calcium Silicate Boards material.
— - Autoclaved Aerated Concrete (AAC)
An overview of the various forms of C-S-H, the
Depending on the production process different molar ratio of CaO/SiO2 and the temperatures at
forms of CSH are purposely produced to which the C-S-H can be synthesized is given in
influence the properties of the building product. the following figure A..

°C

Molar ratio CaO/SiO2

Figure A: C-S-H depending on CaO/SiO2 ratio at various temperatures /1/

2
 Calcium Silicate Hydrate in Fiber Cement Sheets
and Autoclaved Aerated Concrete (AAC)

Among the three production processes for fiber autoclaved building materials are Tobermorite
cement sheets/boards, calcium silicate boards and Xonotlite.
and autoclaved aerated concrete blocks/ panels
only fiber cement sheets can be found either as Wehrhahn offers concepts, production
autoclaved or air cured sheets. Calcium silicate equipment, know-how and services for all
boards and AAC are exclusively hardened by these processes. The following table gives
autoclaving. The relevant forms of C-S-H in basic information on the three processes.

Product Fiber Cement CS Boards AAC

Curing Autoclaved Air Autoclaved Autoclaved
800 - 1800 1200 - 1800
200 - 800 kg/m³ 350 - 800 kg/m³
Density kg/m³ (50 - kg/m³ (75 -
(12,5 - 50 lbs/ft³) (22 - 50 lbd/ft³)
112,5 lbs/ft³ 112,5 lbs/ft³)
Tobermorite, Amorphous, Xonotlite Tobermorite
Type of CSH CSH (I) and poorly CSH(I) and CSH(II)
formed CSH(II) crystallized
form
Cellulose Cellulose, Cellulose None
synthetic
Fibers
fibers (PVA,
— PAN)
Cement Cement Quicklime Cement and
Binders
Quicklime
Silica sand, Usually none, Silica sand, Silica sand or PFA
amorphous sometimes amorphous silicates, or a mixture of both,
silica, perlite, small vermiculate, perlite or mine tailings
Siliceous vermiculite, quantities of
Compounds mica, siliceous
bentonite, compounds
kaolin, slag,
PFA
Flat roofing Corrugated Insulating material Load-bearing or
sheets like roofing sheet, for low and high non-load-bearing
slate or shake external walls temperature wall building
imitation, or facades, applications, fire material, blocks,
sidings, ceilings, protection mega-blocks or
Application external walls separating reinforced panels,
or facades, walls external walls,
ceilings, separating walls,
separating ceilings, roofing
walls, fire
protection

Table 1: Production processes for fiber cement sheets, AAC and CS boards

A summary of the most common processes and II.1 Fiber Cement Sheets/Boards
detailed explanations on all processes can be
found in the Wehrhahn presentation „Process Fiber cement sheets are used for a wide range of
th
Options for the Production of Fiber Cement“ for 6 applications. In table 1 the different applications
International Inorganic-Bonded Wood & Fiber for autoclaved and air cured sheets are explained.
Composite Material Conference 1998. The machines to produce fiber cement sheets are
almost the same for autoclaved or air cured
products.

3
 Calcium Silicate Hydrate in Fiber Cement Sheets
and Autoclaved Aerated Concrete (AAC)

II.1.1 Production Process

Figure B: Production Process: Fiber cement sheets/boards /4/

Cellulose Cutting to size

The cellulose, which mostly arrives in bales, is The sheet needs to be cut to exact size and runs
well refined (fibrillated) with water and stored in a through a cutting system with rotating knives,
cellulose slurry tank. guillotines, water jet cutters or even better
through a high precision cutting press, where the
Dosing and Mixing sheet can be cut to any irregular shape and even
The opened fibers – and for air cured processes nail holes can be punched.
synthetic fibers - are automatically dosed
together with cement, additives, and for Flat, corrugated or embossed
autoclaved sheets with sand slurry, into the The sheet can then remain as a flat sheet or can
turbopulper for mixing with water. The slurry is be corrugated. It can be compressed in a stack or
further diluted with water and runs into each of single sheet press to improve strength and
the sieve cylinder tubs of the sheeting machine. increase freeze-thaw resistance. The sheets can
be embossed in the press to get a pattern on top.
Sheet production Sheets may also be embossed directly on the
The rotating sieve cylinder collects a thin layer of size roller without additional pressing or in a roller
the solid materials whilst most of the excessive press with minimal pressing.
water passes through the wire mesh of the sieve.
The thin layers of all the various sieve cylinders Presses
are collected on the felt, which runs with a speed Wehrhahn offers economic stack and single
of approx. 70 ≥ 120 m/min (230 – 400 ft/min) over sheet presses with specific pressure of 50 –
2
dewatering vacuum boxes to the accumulation 300 kg/cm (700 – 4000 psi).
roller. The size roller accumulates layer after
layer, until the programmed number of Curing
revolutions and the required sheet thickness is After a defined precuring time sheets are ready
reached. The sheet thickness is controlled by an for further handling. They are then demoulded
automatic system, which influences the density of and palletized for two to four weeks air curing, or
the slurry going into the tubs, the felt speed and high pressure steam cured in autoclaves for
other parameters. about 12 hours. The autoclaved sheets are
palletized after autoclaving and are immediately
ready for application.

4
 Calcium Silicate Hydrate in Fiber Cement Sheets
and Autoclaved Aerated Concrete (AAC)

Autoclaved fiber cement sheets require the Sheets with a density ≥800kg/m³ (50 lbs/ft³)
following additional equipment: produced on a sieve cylinder sheeting machine
are called fiber cement sheets.
a. Sand preparation
Silica sand is used instead of 40-50 % of the
cement. The sand is ground with water in a II.2 Calcium Silicate Boards
ball mill to the required fineness. The slurry is
stored in specially designed agitator tanks In this presentation the expression Calcium
and dosed into the mixer. The dosing system Silicate Board is used for products with a density
automatically considers the water solid ratio of of 200 – 800 kg/m³ (12,5 - 50 lbs/ft³). They are
the sand slurry. mainly used as insulating or fire protection
boards. The strength of these products is of
b. Autoclaving minor interest. Thermal insulation, low weight and
Autoclaves and saturated steam of up to fire resistance are the important properties. The
190°C (374°F) and 12 bar (175 psi) are used desired crystal structure is mostly Xonotlite.
for curing thus forming calcium silicate There are also products on the market, which are
hydrates of their unique crystal structure sold as calcium silicate boards, which are
which gives autoclaved calcium silicate produced on a sieve cylinder sheeting machine
hydrates their superior features. as described in chapter II.1 with a density of
approx. 800 - 1000 kg/m³ (50 - 62,5 lbs/ft³).
Qualities/features
Fiber cement sheets are commonly produced in a The production of calcium silicate boards requires
density range of 800 – 1800 kg/m³ extremely pure raw materials with as little
(50 - 112,5 lbs/ft³), mostly 1300 - 1600 kg/m³ impurities as possible. The quality criteria for
(80 - 100 lbs/ft³). these boards is the shrinkage rate and thermal
— The nomenclature to distinguish between fiber conductivity at temperatures >1000°C (1832°F).
cement and calcium silicate boards is not always The lower the shrinkage rate the higher the
clear. Especially fiber cement sheets produced quality of the board. The strength of the sheet is a
on a sieve cylinder sheeting machine with lower minor criteria.
densities (800 – 1200 kg/m³ resp. 50 - 75 lbs/ft³)
mostly applied as versatile fire resistant building II.2.1 Production Process
boards are sold as calcium silicate boards. Three similar processes are known for the
production of calcium silicate boards. The raw
In this presentation it is distinguished between materials are lime, silica, cellulose fibers, water
fiber cement sheets and calcium silicate boards and additives. In all three processes the raw
by density and production process. materials are thoroughly mixed with water.

Figure C: Production Process: Calcium silicate boards /4/

5
 Calcium Silicate Hydrate in Fiber Cement Sheets
and Autoclaved Aerated Concrete (AAC)

a. Pouring the slurry into a mould II.3 Autoclaved Aerated Concrete (AAC)
In this process the slurry is poured into a
mould. The solid content in the slurry is Autoclaved Aerated Concrete is a lightweight
exactly adjusted to meet the specification for load-bearing, extremely well insulating wall
the target density of the finished product. The building material, which is produced in the form of
slurry is dewatered in a filter press. The blocks, mega-blocks or reinforced panels. The
formed board is stacked on specially raw materials are almost the same like for
designed spacers for autoclaving. autoclaved fiber cement and calcium silicate
After precuring the material is autoclaved and boards, however AAC does not contain any
dried. fibers. The density is depending on the
application in ranges from 350 – 800 kg/m³
b. Pre-reaction prior to autoclaving (22 - 50 lbs/ft³).
The raw materials are well dispersed in hot
water in an agitated vessel. The pre-reaction
forms calcium silicate hydrate, mostly CSH (II) II.3.1 Production Process
a water rich gel. The gel-like slurry is
dewatered in filter or stack presses to the Here are some features of AAC:
calcium silicate boards. The cellulose helps to - low weight however high strength
dewater the boards. The formed board is then (load-bearing material)
autoclaved and dried. - saving of foundation costs
- extremely durable
c. Stirred autoclave - fire resistant up to four hours
Similar to the process with pre-reaction the - speedy installation
— raw materials react in an agitated vessel. - economic consumption of energy for heating
Here the vessel is pressurized i.e. the raw and air-condition
materials respectively the slurry is autoclaved
in an agitated autoclave. The final crystal The raw materials are: cement, finely ground
structure of the CSH is produced before the silica sand or pulverized fuel ash, quicklime,
sheet is formed. water and an aeration agent mostly aluminum
powder or paste.
After autoclaving the well crystallized calcium
silicate hydrate is formed to boards in filter or
stack presses. After pressing the boards are
dried and packed.

Figure D: Production Process: Autoclaved Aerated Concrete (AAC) /4/

6
 Calcium Silicate Hydrate in Fiber Cement Sheets
and Autoclaved Aerated Concrete (AAC)

Finely ground sand is mixed with water, cement It is therefore mainly a process fiber and does
and quicklime. At the end of the mixing process not significantly influence the properties of the
aluminum powder is added. The slurry is poured finished sheet. The synthetic fibers provide
into a mould, where the chemical reactions start. the long term strength for the product.
The cement and the quicklime react with water.
The slurry stiffens and the temperature rises. The matrix of an air cured fiber cement sheet
is highly alkaline. Especially if the sheet gets
Simultaneously, the aluminum powder reacts with wet alkalis are dissolved, which attack the
the hydroxides from the quicklime and cement. fibers. The cellulose cannot withstand the
Hydrogen is produced, which expands the mass alkalinity for long. The synthetic fibers used are
and forms uncountable tiny little pores in the special alkali-resistant fibers. In air cured fiber
mass. The mass needs approx. 1-3 hours to cement sheets preferably bleached cellulose is
reach sufficient hardness for cutting. It is used, where lignins are removed, which could
removed from the mould by tilting it upright onto inhibit the cement hydration and the bond
an autoclave pallet and is then moved on a between the cellulose and the CSH matrix.
precision trolley into the cutting machines.
The cutting machines accurately wire cut the b. Autoclaved fiber cement
cake into blocks, panels or slabs using special Autoclaved sheets require more cellulose.
cutting wires. All fresh cut-offs are recycled. The cellulose serves both as a process fiber
and to influence the properties of the sheet.
After cutting the AAC is autoclaved for approx. The fiber used in the autoclaved process is a
12 hours at a temperature of roughly 180-190°C wood fiber. The matrix of an autoclaved sheet
(356 - 374°F) corresponding to a pressure of is hardly alkaline which is a result of the
approx. 12 bar (175 psi). autoclaving. The cellulose fiber is
consequently not attacked by alkalis. Here
After autoclaving the AAC is packed and ready preferably unbleached cellulose is used as
— for sale. the residual lignins protect the fibers during
autoclaving.

III. What are the main differences between Synthetic fibers are not used in the
autoclaving and air curing? autoclaved processes as the synthetic fibers
would deteriorate by the high temperature in
the autoclave.
III.1 Raw Materials
c. Autoclaved Aerated Concrete
In table1 some basic information on fiber cement AAC does not contain any fibers.
sheets , calcium silicate boards and AAC are
given. What are the differences in respect of raw
materials and why are these raw materials used? III.1.2. Siliceous compounds
Dissolved SiO2 and CaO from the binding
III.1.1 Fibers: The fibers used are: materials form crystallized forms of calcium
silicate hydrate during autoclaving. SiO2 is
a. Air cured fiber cement consequently compulsory for autoclaved
The fibers used are wood fibers (cellulose) and materials. The chemistry in the autoclave is more
man made (= synthetic) fibers. The cellulose is detailed explained in chapter III.2.2.
primarily required to produce a sheet on the
sieve cylinder sheeting machine.

Process Fiber Cement Sheet Calcium Silicate Board

Curing air cured autoclaved autoclaved
Cellulose: mostly mostly mostly
bleached or bleached unbleached unbleached
unbleached
Synthetic fibers PVA, PAN none none
PVA, PAN
Alkalinity of the matrix high low low

Table 2: Fibers used in fiber cement and calcium silicate products

7
 Calcium Silicate Hydrate in Fiber Cement Sheets
and Autoclaved Aerated Concrete (AAC)

Fiber Cement Calcium Silicate Board AAC

air cured autoclaved autoclaved autoclaved
Silica
o + o +
(quartz, crystalline)

Amorphous silicates o o + o

Expanded silicates o o + -

Table 3: Siliceous compounds in fiber cement, +: mostly a constituent

calcium silicate boards and AAC o: mostly not a constituent
- : not a constituent

It is obvious that air cured sheets do not need - finer sand reduces the processing time
any silica sand or other forms of silicates. Some - finer sand decreases the degree of crystalli-
air cured sheets however contain little amounts of zation
silica sand or PFA (pulverized fuel ash) or other - finer sand increases the compressive strength
forms of silica. This reduces the alkalinity of the - finer sand increases the shrinkage
matrix and improves the dimensional stability of
the sheets, however the strength seems to suffer, Amorphous silicates are mainly used if they are
when these components are added. readily available as by-products from other
industries (like PFA). Amorphous silicates react
— Autoclaved products preferably contain a with CaO immediately even at lower
crystallized form of silica, e.g. quartz, which helps temperatures (≤ 100°C/212°F) and form water-
to increase the crystallinity of the calcium silicate rich gels. These gels are in some processes
hydrate formed in the autoclave. purposely produced, e.g. in calcium silicate
boards to reduce the density of the product.
Particle size of silica
Important is the specific surface area of the silica.
In most cases the silica sand is ground to the III.1.3 Binders
required fineness by ball milling. Binders used in air cured and autoclaved building
Investigations on the influence of the particle size materials are mainly cement and lime. The
distribution on the chemical reactions in the function of the binders are different in these two
autoclave have come to the following results: processes. Whilst the normal cement chemistry is
applicable for air cured products, binders in
The results are valid for a specific surface area of autoclaved products provide only strength to
2000 – 4000 cm²/g (Blaine). facilitate handling prior to autoclaving. In the
autoclave binders provide the required CaO for
the hydrothermal reactions.

Calcium Silicate
Fiber Cement AAC
Board
air cured autoclaved autoclaved autoclaved
Cement + + - +

Low alkaline cements o - - -

Lime/quicklime - - + +

Table 4: Binders in fiber cement, calcium silicate boards and AAC +: mostly a constituent
o: mostly not a constituent
- : not a constituent

8
 Calcium Silicate Hydrate in Fiber Cement Sheets
and Autoclaved Aerated Concrete (AAC)

Typically in autoclave processes is a mix of - The aluminate phase (C3A) constitutes 5 - 10

Portland cement and finely ground silica sand % of the normal Portland cement clinker. The
(quartz). rapid reaction with water can cause undesirable
rapid setting unless a set-controlling agent , in
AAC contains in addition to the cement quicklime most cases gypsum is added.
as a CaO source. The quicklime is necessary to
provide heat in the mixture. Without quicklime the - The ferrite phase (C4AF) constitutes up to 5 -
gas generation process and the stiffening would 15 % of ordinary Portland cement clinker. The
be inhibited and the whole process slowed down. reaction with water is somewhat variable,
possibly due to differences in composition.
AAC is a low density product (350 – 800 kg/m³ Generally its reaction is fast in the beginning
resp. 22 - 50 lb/ft³). The high porosity of AAC is and intermediate at later ages.
achieved by a gas generation agent, which
expands the mass. Mostly aluminum powder or Setting and Hardening at ordinary
paste is used. The aluminum reacts with the temperature
hydroxides from cement and quicklime. Hydrogen A mixture of cement and water in a proportion,
gas is produced which makes the mass expand. that setting and hardening occurs, is called paste.
The water solid ratio (by weight) is typically 0,3 –
It is obvious that the main differences between 0,6.
air-cured and autoclaved processes is the
reduction of cement respectively binder and an Setting is stiffening without significant
addition of finely ground silica sand. Autoclaving development of strength during the first hours of
produces a crystallized product, therefore the hydration.
CaO/SiO2 ratio is very important as it determines
the type of calcium silicate hydrate produced Hardening is significant development of strength
— (mostly Tobermorite and Xonotlite). which usually is a slower process.

III.2 The chemistry of air curing and high Detailed explanations on setting and hardening of
pressure steam curing cement paste can be found in /2/.

This presentation should mainly focus on Here the practical aspects shall be discussed
practical aspects. However the most significant only.
differences in the chemistry are explained.
The setting and hardening of the cement is
III.2.1 Air Curing /2/ mainly influenced by:
In non-autoclaved fiber cement the cement is the - water solid ratio
binding material. Cement sets and hardens as a - cement surface area
result of the chemical reaction with water. - gypsum content
Portland Cement is a complex mixture of various - chemical composition of the cement; most
components. The complexity of the various significantly the C3A content
chemical reactions taking place during setting - Blaine value
and hardening of cement has forced scientists to - temperature
investigate on the major individual phases and - others like alkalis etc. not to be discussed in
their chemistry. Portland cement clinker has a this presentation
composition of approximately 67 % CaO, 22 %
SiO2, 5 % Al2O3, 3 %Fe2O3 and 3 % of other The water solid ratio has a significant influence
components. It consists of four major phases on the strength development and final strength of
called Alite, Belite, aluminate phase and ferrite the cement paste. A basic rule is: the higher the
phase. water content, the less the final strength. The
question what might be the minimum water
Major cement phases content for a complete hydration of the cement
- Alite (C3S) is the most important component in paste is valid. However, the workability of the
Portland cement clinker of which it constitutes paste needs to be taken into consideration as
50 - 70 %. Alite reacts quickly with water and is well.
the most important constituent concerning
strength development in the cement. The higher the surface area of the cement the
higher the strength. This complies with the higher
- Belite (C2S) constitutes approximately 15 - 20 Blaine value of cement types providing higher
% of Portland cement clinker. It reacts slowly strength, but increases the water demand.
with water thus providing relatively little strength
during the first 28 days of hydration. However The gypsum has primarily an influence on the
Belite increases the strength at later ages setting times as it acts as a set regulator for the
significantly. The strength of pure Alite and pure C3A. Any factor increasing the availability of the
Belite are about the same after one year under Al2O3 will tend to increase the amount of gypsum
comparable conditions. that is required to produce a given effect in the

9
 Calcium Silicate Hydrate in Fiber Cement Sheets
and Autoclaved Aerated Concrete (AAC)

early reactions. The effects on strength are II.2.2 High Pressure Steam Curing /2/3/4/
complex and scientifically not well understood.
The optimum gypsum level is normally decided Saturated steam under pressure (autoclaving)
on the basis of empirical strength tests. does not only accelerate the hardening of cement
or concrete but forms different types of calcium
The C3A content has an effect on the setting of silicate hydrate. As discussed in chapter II the
the cement. The higher the C3A content, the structure of the calcium silicate hydrate formed at
higher the tendency for rapid setting. In practice ambient temperatures is amorphous or poorly
the C3A and gypsum content have to be balanced crystallized. Autoclaved calcium silicate hydrate
to provide optimum properties of the cement. however is mostly well crystallized. The degree of
crystallization depends on the raw materials,
In general: the higher the temperatures, the curing conditions in the autoclave and other
faster the chemical reactions. Same applies for factors.
the cement chemistry. As a rule of thumb: An
increase of 10°C (50°F) doubles the rate of It is generally agreed that crystallization
reaction. decreases drying shrinkage and improves
resistance to chemical attack.
Structure of the CSH formed at ordinary
temperatures Chemical reactions in the autoclave
Many crystalline calcium silicate hydrates are The idea to autoclave building materials is rather
known. Most of them are formed only under old. The first patent for the production of sand-
hydrothermal conditions. Consequently the C-S-H lime bricks was issued 1880 (Michaelis). The first
formed under ordinary temperatures is mostly German standard for these products was issued
amorphous or of poorly crystalline structure. After 1927. The idea to produce light-weight
one year the hydration products of C3S are autoclaved materials was also developed at the
Portlandite (Ca(OH)2) and a nearly amorphous same time. The commercial production of AAC
— calcium silicate hydrate having the properties of a started 1924.
rigid gel. These amorphous forms of C-S-H have
a higher affinity to temporarily bind water in The hydrothermal process in the autoclave is until
contrast to well crystallized forms of CSH. today not fully scientifically understood. The
difficulties to follow up with the process in the
This explains the higher shrinkage rate of air autoclave is mainly due to the „Black Box", i. e.
cured products in comparison to autoclaved the synthesis in the autoclave cannot be
calcium silicate hydrate. observed.
Autoclaving at 180° - 190 °C

Figure E: CSH synthesis in the autoclave /4/

10
 Calcium Silicate Hydrate in Fiber Cement Sheets
and Autoclaved Aerated Concrete (AAC)

The reactions in the autoclave require CaO The molar ratio of the CaO/SiO2 of the
(cement, lime ), SiO2 (silica sand, PFA or others) components is approx. 0,6 – 0,9 for the production
and water. The sequence of the chemical of Tobermorite and approx. 1 for the production of
reactions in the autoclave is generally described Xonotlite.
as follows:
Tobermorite is the desired crystal form in AAC and
1. Dissolution of the Ca(OH)2 in the aqueous fiber cement sheets, is synthesized at temperatures
2+ -
phase (Ca and OH ). above 150°C. Xonotlite, the preferred crystal in
2. Dissolution of the SiO2 in the aqueous phase calcium silicate boards for high temperature
- 2-
(H3SiO4) or (H2SiO4) complexes. application, is produced at temperatures above
3. Chemical reaction of the dissolvents to a 200°C (392°F).
lime-rich form of calcium silicate hydrate
close to the surface of the SiO2 source. A significant influence have impurities in the raw
4. Crystallization nuclei of the CSH complexes materials, which can accelerate or inhibit the
are produced at the interphase between solid formation of the crystallized C-S-H.
SiO2 and the aqueous phase.
5. Diffusion of dissolved SiO2 through the
interphase into the aqueous phase.
6. Further growing of the layer.
7. Stepwise change from lime-rich to lime-poor
phases.
8. Temperature and time of the autoclaving
determine which form fo CSH is produced.

—
Solubility

Figure F: Solubility of Ca(OH)2 and SiO2 in water at different temperatures /2:60/

The CSH synthesis starts with the dissolution of

the raw materials in the aqueous phase.

Solubility of Ca(OH)2 and SiO2

At lower temperatures the solubility of the
Ca(OH)2 in comparison to the SiO2 is far higher.
This is the reason why the initially produced C-S-
H is lime-rich.
At higher temperatures the SiO2 solubility is
increased whilst the solubility of the CaO is
decreased. All the dissolved SiO2 is immediately
consumed.

Consequently the rate of reaction depends on the

availability of dissolved SiO2 only.

11
 Calcium Silicate Hydrate in Fiber Cement Sheets
and Autoclaved Aerated Concrete (AAC)

The following electron micrograph shows a quartz particle surrounded by CSH.

Figure G: A quartz particle surrounded by CSH /4/

What influences crystallinity? - autoclaving creates a completely different

The crystallinity is significantly influenced by the hydrated material, i.e. well crystallized calcium
specific surface area of the silica as explained in silicate hydrates like Tobermorite and Xonotlite.
chapter III.1. Crystallization starts on the surface - Air curing forms mainly poorly crystallized or
of the silica source. Amorphous or very fine silica amorphous calcium silicate hydrates.
reacts immediately, but does not undergo the
steps of transformation to more crystallized forms Low density products are mostly autoclaved as
of CSH as fast as crystallized forms of SiO2. the well crystallized structure provides the
strength, which could not be obtained by air
The presence of some sulfates and aluminates curing. In addition the thermal conductivity of
enhance the formation of Tobermorite, whilst the CSH in comparison to quartz is low, which gives
formation of Xonotlite is inhibited by the presence preference to autoclaved material in comparison
of Al2O3. to air cured products.

Crystallinity in Fiber Cement The low shrinkage in comparison to air cured

The crystallinity in fiber cement is affected by products is an important advantage. Less
the cellulose fibers. The residual lignin in the binders reduce the production costs. The
pulp is attacked during autoclaving. As a investment is higher due to additional sand
consequence the higher the temperature in the grinding and autoclaving.
autoclave and the longer the autoclaving time,
the more severe the affect on the cellulose. Wehrhahn is highly specialized in all types of
Sheets can become extremely brittle after autoclaved products, like fiber cement, AAC and
several autoclaving cycles. Soluble organic calcium silicate boards. Valuable know-how
materials from the pulp do also interfere with and expertise regarding autoclave technology
the chemical reactions in the autoclave. and suitable raw materials are at the buyer's
disposal.
Comparison Autoclaving versus Air Curing
It has been explained, that

12
 Calcium Silicate Hydrate in Fiber Cement Sheets
and Autoclaved Aerated Concrete (AAC)

In the following table the most significant differences between air cured and autoclaved products are
summarized.

Air curing Autoclaving

Production Cost standard lower
Investment Cost standard higher
Working capital standard lower
Alkalinity of matrix standard lower
Thermal conductivity standard lower
Strength standard higher
Shrinkage standard lower

Table 5: Comparison Air-curing and Autoclaving Process

Degree of Crystallization Air cured fiber cement sheets are mainly

Except of calcium silicate boards where approx. produced as corrugated roofing sheets.
50 - 80 % of the material is crystallized, AAC Autoclaved fiber cement sheets are mostly
contains only 30 – 40 % and Fiber Cement only produced as flat sheets. The low shrinkage is
10 -20 % of well crystallized forms of CSH. This ideal for applications like interior ceiling board,
— is partly due to the quality of the raw materials exterior siding and others.
and partly due to the curing process, which is
interrupted before the equilibrium of the chemical Autoclaving or air curing is also related to the
reactions is reached. tradition and the climates in various countries.
Whilst Europe was long time focussing on air
cured products, USA and Australia have always
IV. Conclusion preferred autoclaved sheets.
Autoclaving adds highly preferred features to
building materials. Especially the possibility to Wehrhahn offers equipment and production
produce lightweight materials with high strength know-how for all process options.
and low thermal conductivity and the significant
low shrinkage are features related to autoclaved Wehrhahn know-how is based on the experience
products. This applies in particular for AAC and of many users world wide as well as on the
calcium silicate boards. results gained in its own research.

In fiber cement the air cured and autoclave Wehrhahn can advise investors, which process
process are common. Both processes have their from case to case is best and most economic.
benefits.

Literature:
/1/ Dr.-Ing. H. Gundlach, 1973. Dampfgehärtete Baustoffe.
Bauverlag GmbH, Wiesbaden und Berlin
/2/ H. F. W. Taylor, 1990. Cement Chemistry.
Academic Press, London
/3/ N. Isu/T. Mitsuda, 1994. Autoclaved Lightweight Concrete:
Hydrothermal Reaction and its Influence on the Properties.
Annual Report of the Ceramics Research. Institute of Technology, Vol. 4 (1994)
/4/ Wehrhahn, 1998. Internal R&D Report.

13