Ecocem Use of GGBS Concrete Mixes PDF

UCD School of Architecture, Landscape
and Civil Engineering
Use of GGBS Concrete Mixes for

Aggressive Infrastructural Applications
ENTERPRISE IRELAND
INNOVATION PARTNERSHIP PROGRAMME
PROJECT CODE IP/2008/0540
ECOCEM IRELAND
Executive summary
The case for research into the deterioration associated with water and wastewater
infrastructure has been clearly made. For example in the US alone, the Congressional Budget
Office has estimated that annual investments of up to $20 billion and $21 billion is required
to provide adequate infrastructure for drinking water and wastewater respectively. It is also
estimated that the annual operation and maintenance costs associated with drinking water and
wastewater infrastructure to be in excess of $31 billion and $25 billion respectively. In
Ireland, the Government have previously announced that under the Water Services
Investment Plan, 5.8 billion will be spent on this sector. As such, this represents a
potentially lucrative market that exists both in Ireland and internationally.
Research was conducted into the performance of concrete samples manufactured using a
range of binder combinations which were subjected to aggressive environments selected to
represent the most extreme of conditions they will encounter in service. These included attack
from sulfates and from biogenic sulfuric acid. The test results found that:
In sodium sulfate expansion tests, traditional CEM I cements performed significantly

poorer than all other binder combinations. Samples manufactured using the newer
CEM II/A-L binders displayed increased resistance to sulfate attack but still failed to
meet standard performance criteria.
The samples with the highest resistance to sulfate attack were those that contained
50% or 70% GGSB as a cement replacement level, which displayed very low
expansion levels. This also included superior resistance levels than that obtained using
sulfate-resisting Portland cement.
In all cases deterioration was primarily due to bulging, spalling and warping, most
likely as a result of the formation of gypsum.
When subjected to a 1% sulfuric acid solution (pH 1.3), significant surface corrosion
was observed for all binder combinations. Very little distinction was observed
between the various binder combinations.
The main deterioration mechanism consisted of the formation of gypsum on the
external surfaces of the concrete specimens. This was followed by surface
delamination, some spalling. In the long term a widespread lack of cohesion leads to a
failure mechanism that spreads directly to the core.
The results of this investigation have clearly outlined the cause of concrete deterioration in
wastewater treatment systems and distinguished between degradation due to sulfate attack
and that due to a sulfuric acid attack in this environment. There is a need to train concrete
specifiers in understanding the harsh conditions that these structures will encounter in
service. However for this to be fully realised, the range of aggressive environments
associated with wastewater applications needs quantification.
Dr Ciaran McNally, Project Manager
TABLE OF CONTENTS
1
INTRODUCTION .................................................................................................................... 1
LITERATURE REVIEW ......................................................................................................... 3
EXPERIMENTAL PROGRAMME: MATERIALS AND METHODS ................................. 4
3.1
Experimental Overview .................................................................................................... 4
3.2
Materials and methods ...................................................................................................... 5
3.3
3.4
4
3.2.1
Sodium sulfate expansion tests .................................................................................. 5
3.2.2
Sulfuric acid tests ....................................................................................................... 7
Ultrasonic Tests .............................................................................................................. 10

3.3.1
Review of current research ....................................................................................... 10
3.3.2
Experimental setup ................................................................................................... 11
Permeability tests ............................................................................................................ 13

EXPERIMENTAL PROGRAMME: RESULTS ................................................................... 14
4.1
Overview ........................................................................................................................ 14
4.2
Sodium sulfate expansion results ................................................................................... 14
4.3
Discussion of sodium sulfate expansion results ............................................................. 23
4.4
4.5
4.3.1
Dilution effect .......................................................................................................... 23
4.3.2
Permeability and porosity......................................................................................... 24
4.3.3
The Influence of C3A ............................................................................................... 25
4.3.4
Influence of C3S and C2S ......................................................................................... 27
4.3.5
Sulfate resisting capabilities of CEM II/A-L and GGBS concretes ......................... 27
Sulfuric acid test results .................................................................................................. 29

4.4.1
Mass loss results ....................................................................................................... 29
4.4.2
Discussion of deterioration mechanism ................................................................... 34
4.4.3
Cube strength tests ................................................................................................... 36
4.4.4
Sulfuric acid expansion tests .................................................................................... 37
Ultrasonic results ............................................................................................................ 38

4.5.1
Stiffness loss in due to sulfuric acid testing ............................................................. 38
4.5.2
Stiffness loss in concrete exposed to a 1% sulfuric acid solution ............................ 41
4.5.3
Discussion of ultrasonic results ................................................................................ 46
4.5.4
Microstructural Effects ............................................................................................. 46
4.5.5
4.6
5
Chemical effects ....................................................................................................... 48
Permeability, absorption and sorptivity results .............................................................. 49

DISCUSSION ........................................................................................................................ 51
5.1
Sulfate experimental programme.................................................................................... 51
5.2
Sulfuric acid programme ................................................................................................ 52
5.3
Ultrasonic analysis .......................................................................................................... 54
CONCLUSIONS .................................................................................................................... 56
6.1
Sodium sulfate tests ........................................................................................................ 56
6.2
Sulfuric acid tests............................................................................................................ 57
6.3
Summary......................................................................................................................... 58
1 INTRODUCTION
The deterioration of wastewater infrastructure has long been a cause for concern but the issues
surrounding the problem remained unknown for many years. Traditionally designed to resist high
levels of sulfate attack, wastewater treatment systems are subjected to a considerably more
aggressive form of deterioration biogenic sulfuric acid corrosion. To this day the true
mechanisms of attack have yet to be fully grasped by concrete specifiers and this is evident in the
poor state of infrastructure used in this environment. There is clearly a need to distinguish
between the two forms of attack and the research conducted in this investigation shows that both
the nature and severity of attack is drastically different. Existing methods aimed at counteracting
the corrosive forces focus on remedial work, periodic maintenance and replacement of defective
components. This is clearly not a cost effective practice especially considering that this form of
attack can manifest itself within a relatively short period of time (under ten years).
In examining current European standards one discovers it is not necessarily the fault of the
specifier that integrity of wastewater infrastructure is being compromised at such an early age,
but rather a combination of a lack of understanding of the true mechanisms at work (owing to
largely disjointed research efforts) and a concrete standard that does not adequately distinguish
between the effects of sulfate and sulfuric acid attack. Further research reveals that the current
ability to model sulfate degradation is lacking in both accuracy and reliability meaning adopting
the recommendations of such work would be an unwise course of action. Much of this
uncertainty is reflected by the very complex nature of sulfate attack, and to an extent sulfuric acid
attack. Both mechanisms require an accelerated experimental analysis to monitor their destructive
effects in a reasonable timeframe but by doing so this in turn modifies the nature and severity of
the attack.
In what would appear to be a somewhat Catch 22 scenario, existing recommendations for
these aggressive environments resort to limiting the exposure of concrete to such environments or
increasing cement content while lowering the w/c ratio without truly examining the mechanisms
at work. The need to affect a change in such practice has become more important with the
increased use of secondary cementitious materials in modern concrete practice. The effect of such
additions often modify the chemical composition of a hydrated cement paste making some more
vulnerable than others to aggressive chemical environments. Simply referring to these

constituents as cementitious materials may no longer be adequate terminology.
Taking all of this into consideration, it is clear that the design of wastewater infrastructure
is both imprecise and most likely inaccurate yet it is through the standards that change must come
in order for a greater understanding to be achieved. Using guidelines such as increasing the
cement content cannot justifiably claim to prevent the occurrence of complex corrosion
mechanisms like those of sulfate, sulfuric acid or biogenic sulfuric acid attack. It would appear
that a more complex and precise means of assessing concrete durability for long term exposures
must be thought of. The challenge remains then to transform such a method into a usable tool for
concrete specification.
Existing research efforts on wastewater infrastructure tend to focus on either the cause or
effect of the corrosion phenomenon while paying little attention to forming a solution to the
problem. On the other hand, those examining possible solutions to sulfate or acidic corrosion fail
to understand the biological aspects sometimes at work and the variability of the bacterial attack.
These disjointed efforts remain the primary hurdle in establishing an authoritative direction in
which to lead future research and it is the goal of this investigation to adequately contrast the
separate corrosive phenomenon and to provide the guidance required to affect such a path.
2 LITERATURE REVIEW
A thorough review of the literature was conducted and a review paper was written entitled
Biochemical Attack on Concrete in Wastewater Applications: a State of the Art Review. This
paper was published in the peer-reviewed journal Cement and Concrete Composites and the full
citation for the paper is: O'Connell, M, McNally, C & Richardson, MG (2010) 'Biochemical
attack on concrete in wastewater applications: a state of the art review'. Cement and Concrete
Composites, 32 (7):479-485. The paper is attached as an Appendix to this report.
This study found that international research to date has focussed on three distinct topics in the
study of sulfate/sulfuric acid effects on concrete. These are:
Studies of the biological processes behind the corrosion of wastewater infrastructure, with
particular reference to the role of sulfate-reducing and sulfur-oxidising bacteria.
Studies of the chemical effects of sulfates and sulfuric acid on concrete mixes
Laboratory-based research methodologies, especially those incorporating the biological

effect on concrete.
It was concluded that chemical tests alone do not fully represent the microbial effects on
concrete, although they may help in assessing the types of damage that can occur. Some
researchers have carried out full-scale laboratory analysis, but it is worth noting that the
equipment necessary to adequately mimic in-situ conditions is invariably complicated,
cumbersome and custom built. The realisation of resources required to undertake such research
continues to be an obstacle to addressing this topic. The use of such complex research apparatus
in routine performance-based specification is impractical.
Although there exists significant quantities of data on the topics of sulfate, sulfuric acid and
biogenic corrosion of concrete, little has been achieved in the way of formulating an accepted
mathematical model of deterioration that incorporates agreed parameters of significance. This
represents a significant knowledge gap and acts as a technical barrier towards using material
design as a means of controlling corrosion due to biochemical attack. This continues to inhibit the
design of durable concrete wastewater infrastructure and has significant implications for public
expenditure in this area. The need to consider the interaction of biological and chemical processes
may hold the key to achieving greater progress and allow practitioners to use concrete mix design
as a means of delivering intended service lives.
3
3 EXPERIMENTAL PROGRAMME: MATERIALS AND METHODS

3.1 Experimental Overview
The aim of this investigation is to examine the behaviour of concrete and mortar in aggressive
chemical environments containing sulfate and sulfuric acid with a view to recommending a
specification that can be used to optimise the expected service life in such harsh conditions.
Specimens containing cement replacement levels of 0 %, 50% and 70% with ground granulated
blast-furnace slag (GGBS) were tested along with a sulfate resisting Portland cement mix. The
materials used for this investigation were locally sourced and consisted of sand, CEM II-A/L
limestone cement, CEM I ordinary Portland cement, sulfate resisting Portland cement, granulated
ground blast-furnace slag (GGBS) and coarse limestone aggregate graded 10mm and 20mm
(Table 3.1). The test programme comprised monitoring performance through:
Sodium sulfate expansion tests
Sulfuric acid tests
Ultrasonic tests
Table 3.1 Experimental materials
Material
Sulfuric Acid Tests
Sodium Sulfate Tests
Sand
Hanlons, Co. Kildare
CEN-Normensand
(DIN EN 196-1)
Cement
Cement replacement
Coarse Aggregate
CEM I, CEM II/A-L, SRPC
CEM I, CEM II/A-L, SRPC
GGBS
GGBS
(0%, 50% & 70%)
(0%, 50% & 70%)
10mm & 20mm
None
Belgard limestone
Water
Tap water
Tap water
3.2 Materials and methods

3.2.1 Sodium sulfate expansion tests
A modified ASTM C1012 procedure was used to test the mortar prisms for change of length
when exposed to a sulfate solution. The modification consisted of recording comparator
measurements on a fixed 28-day interval for the duration of the analysis. Mortar prisms of
dimensions 285mm x 25mm x 25mm (Figure 3.1) were prepared through use of the standard mix
in EN196-1 for cement conformity testing. Each mix contained 450g of binder, 1350g of sand
(CEN-Normensand DIN EN 196-1) and 225g of water and produced four prisms. The freshly
cast specimens were placed in a moist air cabinet at 20C and demoulded after twenty-four hours.
Following demoulding they were immersed in a water bath at 20C and allowed to cure until an
age of twenty-eight days.
Table 3.2 Mix designations
Mix Designation Cement Type
% GGBS
MA
CEM II/A-L
MB
CEM II/A-L
50
MC
CEM II/A-L
70
MD
CEM I
ME
CEM I
70
SR
SRPC
The standard exposure solution used in this test method contains 50g of sodium sulfate
(Na2SO4) per litre of distilled water. Each solution was prepared with 4.5l of distilled water and
mechanically stirred until fully dissolved. The solution was then topped up with distilled water
until a volume of 5l was achieved. It was then placed into a standard domestic polyethylene
container ensuring the quantity was sufficient to cover the prisms by a minimum of 5mm.
Figure 3.1 Example of the ASTM C1012 standard mortar prisms

The prisms were stored for a period in excess of one year and the solution was refreshed on
a monthly basis. This consisted of the disposal of the spent solution, the storage tank rinsed with
water and a fresh sodium sulfate solution prepared as previously detailed. Comparator readings
were taken every four weeks. The readings consisted of taking an initial reference measurement
for each prism and a standard reference invar bar prior to immersion in the sodium sulfate
solution. The change in length of the prism is recorded with reference to the initial reading and is
then calculated according to:
=
100
Eqn. 1
L = change of length at age x (%)

Lx = comparator reading of specimen at age x reference bar comparator reading at age x
Li = initial comparator reading of specimen reference bar comparator reading at the same time
Lg = nominal gauge length or 250mm as applicable
The percentage change of length of each prism was expressed to an accuracy of 0.001%
and the average of the four test specimens was recorded. A photographic record of the prisms was
6
carried out at eight week intervals to document any change in the physical appearance of the
specimens.
Figure 3.2 Comparator reader with reference bar
3.2.2 Sulfuric acid tests

The aim of the experimental programme was to assess the performance of six different concrete
mixes exposed to environmental conditions similar to those found in wastewater treatment plants.
The cubes were immersed in a 1% sulfuric acid solution for six months and monitored for mass
loss, expansion, visual appearance and compressive strength. Three of the mixes consisted of
CEM II-A/L limestone cement with 0%, 50% and 70% additions of GGBS as a cement
replacement, two contained CEM I Portland cement with 0% and 70% GGBS while the final mix
was a standard sulfate resisting SRPC mix. The performance of GGBS in an acidic environment
was of particular interest while the performance of limestone cement remains largely
undocumented in this type of aggressive environment.
7
Fourteen concrete cubes measuring 100mm were cast for each mix with varying
percentages of GGBS as a cement replacement indicated in Table 3.2. The water / binder ratio
was specified at 0.45 and binder content at 360kg/m3 to represent the limitations permitted under
exposure class XA3 (>3000mg/l and 6000 mg/l SO42-; pH 4.5 and >4) as detailed in IS/EN
206-1. Simultaneously, four prisms measuring 250mm x 75mm x 75mm were also cast with each
of the different mixes. The mix proportions for each set of cubes are outlined in Table 3.3.
Table 3.3 Concrete mix quantities for sulfuric acid tests

Quantities (kg/m3)
Mix
Type
Cement
GGBS
C20
C10
aggregate
aggregate
Sand
Water
F/(F + C)
Volume
(m3)
MA
CEM II/A-L
360
810
405
685
162
0.361
0.985
MB
CEM II/A-L
180
180
805
400
680
162
0.361
0.984
MC
CEM II/A-L
108
252
805
400
680
162
0.361
0.986
MD
CEM I
360
810
405
685
162
0.361
0.985
ME
CEM I
108
252
805
400
680
162
0.361
0.986
SR
SRPC
360
810
405
685
162
0.361
0.985
Notes:
F = Fine aggregate; C = Coarse aggregate
Volume = Volume fraction of cube space occupied by solid matter
SRPC = Sulfate resisting Portland cement
All of the cubes were stored in a curing tank at 20C for twenty-eight days following which
the strength of cubes 1 and 2 for each mix was tested under compression until failure. The
remaining twelve cubes were now divided into two sets of six split between continued storage in
the curing tank and immersion in a 1% sulfuric acid solution at pH1.5 for up to 168 days. The
dimension of each cube was also recorded prior to commencing the analysis. Table 3.4 shows the
experimental schedule adopted for the test programme. The samples were brushed with a wire
brush every seven days under running water which resulted in a milky-white runoff. Brushing
was ceased when the runoff colour reverted to clear water. All cubes were weighed every seven
8
days for the first month and every twenty-eight days thereafter to record any mass loss or mass
gain. For those stored in the sulfuric acid solution loosely adhering corrosion products were
brushed away prior to recording mass.
Table 3.4 Storage and test conditions adopted for the brushed programme
Cube No.
1, 2
Storage Condition
Mass Readings
Compression Test
28 days curing water @20C
7, 14, 21 & 28 days
After 28 days curing water @20C
7, 14, 21, 28 days, then
After 28 days storage water @20C
ONLY
3, 4
28 days storage water @20C
every 28 days
9, 12
28 days storage acid @20C
7, 14, 21, 28 days, then
After 28 days storage acid @20C
every 28 days
6, 7
56 days storage water @20C
7, 14, 21, 28 days, then
After 56 days storage water @20C
every 28 days
10, 13
7, 14, 21, 28 days, then
After 56 days storage acid @ 20C
every 28 days
5, 8
168 days storage water@20C
7, 14, 21, 28 days, then
After 168 days storage water@20C
every 28 days
11, 14
7, 14, 21, 28 days, then
After 168 days storage acid @20C
every 28 days
The sulfuric acid solution for all experimental schedules was maintained at a pH of
approximately 1.5 by titrating the solution with a more concentrated sulfuric acid to keep the pH
within a margin of 0.3. The solution was refreshed once a month to avoid prolonged
contamination associated with the corrosion products of degraded concrete.
A second set of mass loss experiments was undertaken over a twelve-month period
exploring the effect that brushing the specimens, to remove loosely adhering corrosion particles,
has on the attack rate. To this end, a further twelve specimens were cast (two for each respective
mix) and their mass recorded every seven days for the first twenty-eight days and again every
twenty-eight days thereafter until one hundred and sixty eight days exposure was achieved. The
9
cube strengths were also determined for each of the samples after one hundred and sixty eight
days. The technique in the first programme has already been outlined while the second technique
involved no weekly brushing. The specimens were briefly held under running water once a
month, however, before being immersed in a fresh solution of sulfuric acid. The principle behind
each brushing technique was to not only assess the behaviour in two extreme abrasion conditions
for both stagnant and flowing water but also to attempt to mimic the severity of the bacterial acid
attack.
Finally, a parallel experimental regime was carried out to investigate the change of length
of the concrete prisms exposed to the same sulfuric acid solution while adopting an identical
weighing and weekly brushing technique as in Table 3.4. For this, following twenty-eight days
curing, two prisms from each mix were immersed in the sulfuric acid solution while a further two
remained stored in water. An initial reading for each prism was performed prior to immersion
with a standard reference invar bar and subsequent readings taken at twenty-eight day intervals.
The technique and calculations were performed according to those outlined for the sodium sulfate
expansion tests.
Table 3.5 Test conditions for prisms exposed to 1% sulfuric acid

Prism
Storage Condition
Mass Readings
Comparator Readings
168 days storage water
7, 14, 21, 28 days, then every 28
Every 28 days following
@20C
days
curing
7, 14, 21, 28 days, then every 28
Every 28 days following
days
curing
No.
1,2
3,4
Note: All prisms adopted an identical curing regime of 28 days in water at 20C following which they were exposed
to the storage condition outlined above
3.3 Ultrasonic Tests

3.3.1 Review of current research
Ultrasonic non-destructive testing of concrete possesses a clear time and resources advantage
over traditional methods but often depends on careful interpretation of the results. In the context
10
of promoting high levels of cement replacement materials, the advantages and disadvantages
should be acknowledged. While high replacement levels will have inherent benefits such as a
denser microstructure or the ability to reduce the carbon footprint of a building, they also have
some drawbacks, the most prominent of which is slower initial gain of strength. The development
of a reliable ultrasonic technique to monitor the development of stiffness in early age concrete
would allow us to work with this material property. This was the basis of a research paper that
was presented at a Geophysics conference in Dublin in 2009. This paper described how a method
was developed at UCD that would allow us to use ultrasonic testing to detect the rapidly
occurring changes in the modulus of early age concrete. The full citation for this paper is:
O'Connell, M, McNally, C, Donohue, S, Bonal, J & Richardson, MG (2009) Assessment of
ultrasonic signals to determine the early age properties of concretes incorporating secondary
cementitious materials. In: Proceedings of the 15th European Meeting of Environmental and
Engineering Geophysics, Dublin, 7- 9 September. A copy of the paper is included in Appendix B
of this report.
3.3.2 Experimental setup

The benefit of this work is that while a proven ultrasonic analysis technique can be used to chart
stiffness development in hydrating concrete, it may also be used in monitoring stiffness loss in
concrete subjected to a corrosive environment. During a chemical attack concrete undergoes a
significant alteration of its internal microstructure leading to a loss of strength and ultimately
failure. Often the effects of a sulfate attack, for instance, can only be realised when the
phenomenon has reached a substantial stage of progression. Ultrasonic analysis has the potential
to detect degradation at an early stage and its benefits could be exploited in the monitoring of
critical transport and water infrastructure whether it bridge foundations exposed to aggressive
ground sulfate levels or biogenic sulfuric acid corrosion in wastewater treatment systems. The
ultrasonic investigation of each of the cube specimens required S-wave (transverse shear waves)
and P-wave (longitudinal waves) ultrasonic readings to be taken every twenty-eight days
following immersion in acid. This was maintained for one hundred and sixty eight days. Squareshaped plastic caps measuring 50mm were attached to two sides of the cubes subjected to
ultrasonic testing and the edges sealed with a mastic glue. This ensured a region protected from
exposure to acid / corrosion on which to place the ultrasonic transducers and obtain a reading.
11
Two sets of transducers were used for this purpose in conjunction with a square wave pulserreceiver in through-transmission mode (Figure 3.3). The S-wave transducers had a frequency of
100 kHz, the P-wave transducers 50 kHz.
Figure 3.3 Ultrasonic testing equipment (L-R): Laptop, digital oscilliscope, signal generator,
100mm cube with ultrasonic transducers and ultrasonic couplant
For both S-wave and P-wave measurements each transducer was coupled directly opposite
the other using a shear wave couplant gel as this was found to give excellent acoustic properties
for both wave forms. It was essential to ensure a good connection between the couplant and the
concrete as this was found to affect the amplitude of the signal. A 100V amplitude pulse was
emitted into the specimen and the signal allowed to settle. The signals were recorded using a
digital oscilloscope connected to a laptop computer and the results analysed with a Python shear
wave detector algorithm to aid in the detection of the first arrival point (Bonal et al., 2010). An
identical procedure was applied to the specimens used to investigate the effects of brushing with
regular measurements taken at twenty-eight day intervals.
12
3.4 Permeability tests

A series of air permeability, water permeability and water sorption tests were carried out on two
samples each of the six concrete mixes using the Autoclam permeability system (Figure 3.4). A
base ring is attached to the sample and affixed to the apparatus rendering it air/water tight. The
apparatus operates on the following principle: for air permeability, the pressure inside the
apparatus is increased slightly to 0.5 bar and the decay of it is monitored every minute from 0.5
bar for 15 minutes or until the pressure has diminished to zero. A plot of the natural logarithm of
pressure against time (mins) is linear. The air permeability index is taken as the slope of the
linear regression curve between 5 and 15 minutes. For water permeability, water is introduced to
the apparatus test area and the pressure is increased to 0.5 bar where it is maintained for the
duration of the test. The quantity of water flowing through the concrete is measured and a straight
line is plotted of the former against the square root of time between the 5th and 15th minute. A
similar regime is implied for the water sorption test however the test pressure is reduced to 0.02
bar and kept constant for the test duration.
Figure 3.4 Autoclam permeability system with controller on the left and the unit (in blue) on
top of the specimen
13
4 EXPERIMENTAL PROGRAMME: RESULTS

4.1 Overview
This section presents the results of the experimental data obtained for the sodium sulfate
expansion tests, sulfuric acid tests and the ultrasonic analysis testing programme. The percentage
expansions were recorded in the sodium sulfate testing programme in conjunction with a detailed
visual description of the test specimens. A variety of observations are discussed, compared and
contrasted with reference to each of the mixes and an analysis carried out to ascertain the
contributing factors towards their performances. The sulfuric acid tests employed a similar visual
recording and discussion methodology in addition to other parameters being examined including
mass loss, cube strengths and expansion. The ultrasonic testing programme is applied to monitor
the loss in stiffness following exposure to a 1% sulfuric acid solution over a six month period.
The results are compiled and discussed with reference to each mix and their relevant chemical
and physical performance factors.
4.2 Sodium sulfate expansion results

The sulfate expansion tests were carried out as detailed in section 3.2.1 where the solution was
refreshed on a twenty-eight day cycle, maintained at room temperature and the pH of the system
was uncontrolled. Figure 4.1 shows the results of the test program as measured in percentage
expansion according to
Eqn.
1.
The
average
expansion of four prisms was used to obtain the data points in Figure 4.1.
Expansions were obtained for a twelve month period for all six mixes while subsequent
measurements were carried out for some. Early exposure (up to 84 days) for specimens MA, MB,
MC, ME and SR showed an identical trend of expansion registering little movement. MD
however, is already showing greater expansion in comparison and this mix shows a continuing
acceleration of the phenomenon. At one hundred and twelve days MA can be observed to show
an inferior resistance to the aggressive solution compared with MB, MC, ME and SR. Both mixes
MA and MD contain no addition of GGBS. Mix MD is ordinary Portland CEM I cement while
mix MA represents Portland CEM II-A/L limestone cement. At one hundred and ninety six days
exposure, both mixes ME and SR are beginning to show minor deviations from the continuing
minimal expansion rate of mixes MB and MC.
14
Sulfate Expansion Tests
% Expansion
0.9
0.8
CEM II 100%
CEM II + 50% GGBS
0.7
CEM II + 70% GGBS
CEM I 100%
0.6
CEM I + 70% GGBS
SRPC 100%
0.5
0.4
0.3
0.2
0.1
0
0
56
112
168
224
280
336
392
448
504
Days Exposure
Figure 4.1 Mortar prisms expansions following immersion in a 5% sodium sulfate solution
Table 4.1 American Concrete Institute (ACI) performance guidelines for concrete exposed to
sulfate when tested according to ASTM C1012.
Exposure
Level
Exposure
Class
Dissolved sulfate in
water (ppm)
Max Expansion When Tested Using ASTM

AS
C1012
At 6 months
Moderate
S1
150 SO42- 1500

(Seawater)
0.10%
Severe
S2
1500 SO42- 10000
0.05%
Very severe
S3
>10000
At 18 months
At 18 months
0.10%*
0.10%
*The 12-month
month expansion limit applies only when the measured expansion exceeds the 6-month
month expansion limit
Mix ME is a 30% Portland CEM I cement with 70% GGBS while SR is a Portland CEM I sulfate
resisting cement. Mixes MB and MC are both CEM II-A/L
A/L limestone cement mortars with 50%
and 70% replacement levels of GGBS respect
respectively.
ively. At three hundred and eight days exposure,
15
the sulfate resisting mortar SR has now begun to expand beyond the level of mix ME leaving the
three mortars with GGBS as a cement replacement showing the least expansion.
There were some marked differences in visual deterioration of the mixes varying from
corrosion related deposits and discoloration to cracking and warping of the specimens, or a
combination of each. The severity of the visual deterioration corresponds well to the degree of
expansion observed. Examination of each of the test mortar prisms indicated the formation of
longitudinal cracks around 0.035% - 0.04% and this was common to all mixes having reached
this expansion level (Figure 4.3, Figure 4.4 & Figure 4.6). Figure 4.3 and Figure 4.4 show these
longitudinal white-filled cracks along the edges of both the SRPC and CEM II 100% specimens.
The CEM I specimens (both MD and ME) show a similar crack formation although lacking in
any white substance (Figure 4.5 & Figure 4.6). The remaining specimens containing GGBS (MB
and MC) have not yet shown any crack formation.
Longitudinal cracking along the length of the specimens was not an exclusive mechanism
with radial cracking observed on one of the MA specimens along the boundary of the reference
stud (Figure 4.2a). One of the other visual distinctions between MA and MD were notable
depositions of a white substance occurring in blotches at random intervals on one of the prisms
which can be seen in Figure 4.2b. These deposits seemed to be an integral part of the paste and
were not soft to touch, nor had they the ability to be removed by scratching the surface.
(a)
16
(b)
Figure 4.2 Radial cracking observed around the reference studs (a) and white blotches
appearing on the surface of the prism (b)
Generally however, the appearance of white deposits was less locally concentrated than in
Figure 4.2b and consisted primarily of an intermittent speckled pattern throughout the prisms.
This was applicable to all specimens and mixes after one year except those containing 70%
GGBS as a cement replacement.
Of the specimens whose deterioration has reached an advanced stage (approximately 0.1%
expansion or greater - MA and MD), an increase in the crack density / length appears to be a
common occurrence combined with the earnest commencement of corner spalling. Figure 4.7 (a)
& (b) below show missing corner edges on specimens from mix MA and MD at an approximate
expansion value of 0.1%. There is some evidence of rounding of the edges on specimens SR
and ME however they have not reached the extent of spalling observed below.
17
Figure 4.3 White filled crack drawn parallel to yellow line and indicated by red arrows (SR)
Figure 4.4 White filled crack drawn parallel to yellow line and indicated by red arrows (MA)
18
Figure 4.5 Longitudinal crack drawn parallel to yellow line and indicated by red arrows (ME)
Figure 4.6 Longitudinal crack indicated by red arrows (MD)

19
(b)
Figure 4.7 Spalling of MA (a) and MD (b) prisms at 0.1% expansion
Simultaneous to this process, increased radial expansion could be observed to begin on

some specimens between approximately 0.2% expansion and 0.45% expansion around the
reference stud (Figure 4.10). Although this stage of deterioration was particularly visible for mix
MD, the initiation of radial cracking was also observed on one on the specimens from mix MA,
as seen in Figure 4.2a, suggesting that this process may be replicated once expansion has reached
an equivalent level.
Figure 4.8 Spalling of the corners and loss of cohesion of the CEM I mix (MD) after one years
exposure
Continuing corrosion could be observed on specimens MD as the acceleration of the
degradation process had significantly advanced with this mix after sixty-four weeks. At fifty-two
weeks exposure and an expansion of approximately 0.3%, a slight warping of one of the prisms
was observed along with the propagation of a crack perpendicular to the surface. At sixty-four
20
weeks the crack had significantly developed and extensive warping was visible (Figure 4.9). This
perpendicular cracking occurred for prisms MD3 and MD4 as these individually had the most
advanced level of expansion.
(b)
(c)
Figure 4.9 (a-c) Perpendicular crack propagation in mix MD
21
(b)
Figure 4.10 Onset of extensive radial crack / bulging
Visually, both mixes MA and MD appear to have suffered the most. Cracking and spalling
was widespread after one year for both with white deposits seemingly a prominent feature for the
attack on MA while MD exhibited almost exponential expansion. Mixes MB and MC, the CEM
II/A-L limestone cements with 50% and 70% GGBS respectively, have shown comparatively
little expansion and little differentiation. MB has shown some minor discoloration while MC has
shown no visual evidence of attack. The sulfate resisting cement specimens (SR) have been
outperformed by all mortars containing GGBS either with CEM I or CEM II/A-L after one year.
Visually it has begun to exhibit the same common degradation phenomenon when approaching
0.030% 0.035% expansion, namely cracking, spalling and a white speckled appearance (the
latter, however, generally beginning to appear within eight weeks).
It can be concluded that within the given testing parameters, there is a clear benefit to the
addition of a high percentage ( 50%) of GGBS to mortar. This would seem to be the case
regardless of the cement type used although it would appear to have a greater contribution in
increasing the resistance of CEM I mixtures to sulfate attack. The CEM II/A-L limestone cement
used in this experimental programme exhibits an inherent sulfate resisting capability although
may not be sulfate resistant. When combined with a percentage of GGBS greater than or equal to
50% the resulting mixture exhibits a superior level of sulfate resistance to that of all others tested,
including a standard sulfate resisting Portland cement.
22
4.3 Discussion of sodium sulfate expansion results

Traditionally cements supplied to the Irish market have been of the CEM I variety, however since
2007 there has been a significant change in Irish concrete practice. With manufacturers becoming
concerned at the energy requirements in traditional (CEM I) production and the resulting carbon
footprint, CEM II/A-L cements with additions of approximately 7% limestone have now become
the dominant cement type. This change needs to be incorporated into concrete specification
particularly for projects exposed to chemically aggressive environments. More importantly, the
effect of a chemical attack needs to be sufficiently documented, outlining failure mechanisms and
potential consequences.
The study conducted in this experimental programme looked at the chemical effects that
concrete and mortar may be exposed to at high sulfate levels. The results have indicated that the
CEM II/A-L limestone cement, as used here, appears to possess an inherent sulfate-resisting
capability which can be further enhanced with the addition of 50% or 70% GGBS as a cement
replacement. Existing research on the effect of limestone additions to cement has indicated wideranging consequences varying from beneficial to detrimental (Gonzlez and Irassar, 1998, Irassar
et al., 2000). Nonetheless a common conclusion seems to centre on an upper limit that provides
an improved resistance and this seems to vary between 15% and 20% (Ramezanianpour et al.,
2009, Irassar et al., 2005). This varying behaviour has been attributed to several possibilities
amongst which are: the dilution effect of cement constituents, permeability and porosity, the
influence of the level of C3A on the system and the level of C3S C2S and calcium hydroxide (CH)
in the hydrated cement paste.
4.3.1 Dilution effect

The dilution effect is simply used to describe the replacement of clinker with a non-cementitious
filler material such as limestone. The latter shows no pozzolanic properties and thus does not
produce C-S-H gel, the main binding component of a hydrated cement paste (Ramezanianpour et
al., 2009). The effect reduces the amount of hydration products reacting during a sulfate attack
and has been attributed by some authors as contributing to the improved resistance in cements
containing minor limestone additions (Hooton, 1990, Gonzlez and Irassar, 1998). This
improvement can be further enhanced by ensuring the C3A content of the cement is minimized.
23
In the sulfate resistance testing described in the previous section, the C3A values for the CEM I
and CEM II cements were 12.3% and 8.4% respectively as derived from Bogues calculations.
While neither value constitutes levels associated with a sulfate-resisting specification, the
reduced percentage may partly account for the better performance of CEM II mixes in the
experimental programme. Nonetheless, several authors have noted the poor performance of
limestone cements even with moderate C3A levels. With this in mind, and given the results
presented, the effect of the percentage limestone added should be given considerable attention.
Table 4.2 Cement chemical analysis
Composition (% by oxides)
Compound
Bogue Equations:
CEM I:
CEM I
CEM II/A-L
CaO
60.29
61.18
SiO2
18.24
18.05
Al2O3
6.19
5.46
Fe2O3
2.45
3.61
MgO
3.55
3.66
Mn3O4
0.26
1.15
TiO
0.00
1.28
Na2O
1.17
1.02
K2O
1.32
1.60
P2O5
4.15
0.00
SO3
2.38
2.99
C3 A =
2.65(Al2O3) 1.69(Fe2O3)
C3 A =
2.65(6.19) 1.69(2.45)
=
CEM II/A-L:
C3 A =
=
12.3%
2.65(5.46) 1.69(3.61)
8.4%
4.3.2 Permeability and porosity

There are clearly other questions regarding the nature of the reaction of limestone with both the
cement paste and sulfate ions. Issues surrounding the effect on permeability, porosity and
24
tortuosity are all topics that have been discussed by several authors (Hornain et al., 1995, Tsivilis
et al., 2003, Pipilikaki et al., 2009). It should also be noted that the effective w/c ratio also
increases with an increasing percentage of filler used and this can be attributed to the lack of
pozzolanic properties of limestone (hence it cannot be considered a cementitious material).
According to Gonzalez and Irassar (1998), the capillary porosity depends on the w/c ratio and the
hydration degree and thus this affects the overall porosity of the cement. Tsivilis et al. (2003)
showed that a Portland limestone cement exhibited lower water permeability values when
compared to an ordinary Portland cement; they added however that permeability is not simply a
function of porosity but also of the size, distribution, shape, tortuosity, and continuity of the
pores. Their tests were carried out on specimens that contained a range of between 0% and 35%
limestone. Pipilikaki et al. (2009) however conducted tests that showed Portland limestone
cement containing 35% limestone had a higher porosity than an ordinary Portland cement. The
authors then suggested that this may indicate a higher permeability, thus contradicting Tsivilis et
al. (2003). They make the observation however, that limestone cements have an absence of large
capillaries which may delay the ingress of sulfates and lower initial expansion but stress that the
mechanism by which limestone affects the sulfate resistance of cement is far from being well
understood.
Whether it is due to a decrease in permeability, the absence of large capillaries or simply
the resultant of the dilution effect, what is clear is that the results presented in section 4.2 indicate
a benefit of using CEM II limestone cement with a filler content of between 5 and 10%. The
addition of 50% or 70% GGBS as a cement replacement further enhances the sulfate resisting
abilities and can more than likely be attributed to not only a decrease in permeability associated
with GGBS but also the reduction in calcium hydroxide in the hydrated cement paste.
4.3.3 The Influence of C3A

The level of C3A in the cement is clearly an important characteristic of its sulfate resistance. It is
a compound that contributes little or nothing to cement strength except at early ages where it is
responsible for flash set. It does however, act as a flux and reduces the temperature of burning
clinker and allows the combination of lime and silica (Neville, 1995). Limiting the amount of
C3A in the system reduces the monosulfate (Afm) phase that can lead to the formation of
25
ettringite. This compound greatly contributes to the expansion of cementitious materials and,
along with gypsum formation, is one of the principal sulfate attack mechanisms. Minimising the
amount of C3A forms the basis of a sulfate resisting Portland cement. However, given that all
mixes containing GGBS as a cement replacement exceeded the performance of SRPC mortar
specimens in the experimental programme, it is clear that reducing the potential for ettringite
formation should not be the only preventative measure taken against a sulfate attack.
Examining CEM II cements, the presence of limestone alters the hydration reactions of
C3A according to several authors. Firstly, ettringite formation is accelerated by the presence of
CaCO3 (Bonavetti et al., 2001) and secondly the reaction between the limestone and C3A forms
carboaluminates (Gonzlez and Irassar, 1998) which compete with monosulfoaluminate stability
and ettringite transformation. With this in mind it is evident that the addition of limestone further
complicates the already complex process of sulfate attack. Gonzalez and Irassar (1998) also
highlight that a high level of C3A extends the interaction of sulfate ions with unstable hydrates in
the mortar. As previously discussed, the level of C3A in both the CEM I and CEM II mixes in the
experimental programme were 12.3% and 8.4% respectively. The 100% CEM I specimen (MD)
showed expansion at one year that was more than three times that of a 100% CEM II specimen
(MA). The inclusion of GGBS as a cement replacement has demonstrably affected the sulfate
performance as evidenced by the low expansion of mixes MB, MC and ME. It has been claimed
that a higher replacement level of a pozzolanic material dilutes the C3A, reduces the aluminate
phases and decreases ettringite formation (Al-Dulaijan et al., 2003, Gonzlez and Irassar, 1998).
Deterioration in limestone cements has primarily been attributed to gypsum formation while the
mechanism in ordinary Portland cements is dominated by ettringite formation (Pipilikaki et al.,
2009). Irassar et al. (2003) further supports this claim by observing greater gypsum formation in
moderate C3A limestone cements subjected to a 5% sodium sulfate solution as specified in
ASTM C1012.
The concentration of the sodium sulfate solution is also important in deciphering the
dominant form of attack. In solutions with sulfate levels exceeding 8g/l the mechanism is said to
be primarily due to gypsum formation (Hekal et al., 2002, Tosun et al., 2009). The tests carried
out in the sulfate expansion programme contained a sulfate strength of 33.8g/l, more than
exceeding the accepted threshold. This may be further supported by the visual observations of
substantial white deposits on the CEM II limestone specimens. With the CEM I mortars however,
26
the situation may be less clear. Although the solution strength would dictate a gypsum dominated
attack, the deposits of the white substance were considerably less than on the limestone mortars
while cracks tended not to be characterised by white veins.
4.3.4 Influence of C3S and C2S

Both the C3S (alite) and the C2S (belite) contents of the cements are also important indicators of
performance under a sustained sulfate attack. The presence of a limestone additive, such as that in
CEM II-A/L, also modifies the Ca/Si ratio of the C-S-H phase, with the interaction of CaCO3
accelerating the hydration of the C3S content (Ramezanianpour et al., 2009). Alite and belite play
important roles in characterising the strength of a hydrated cement paste, the former contributing
much towards strength at early ages, the latter developing those characteristics as time
progresses. However with an increasing percentage of C3S, the quantity of calcium hydroxide
formed during hydration also increases raising a cements vulnerability to gypsum formation
during a sulfate attack (Ramyar and Inan, 2007). Research conducted on pure C3S cement pastes
also demonstrated that even gypsum formation caused considerable expansion (Tian and Cohen,
2000), although this mechanism of attack for cements used in practice is, by the authors own
admission, still a cause for considerable debate . Tosun et al. (2009) observed that cement with a
high percentage of limestone and a high C3S/C2S ratio was more prone to attack by sulfates,
however their use of an extraordinarily high sulfate solution (200g/l SO42-) means their
conclusions must be greeted with some scepticism. It is generally regarded that a cement low in
C3S and C3A will perform well during a sulfate attack; nonetheless this may be difficult as it has
been pointed out that reducing the C3A content raises the C3S/C2S ratio (Al-Dulaijan et al., 2003).
4.3.5 Sulfate resisting capabilities of CEM II/A-L and GGBS concretes

Portland limestone cements suffer similar chemical reactions from a traditional sulfate attack as
ordinary Portland cements resulting primarily in the formation of gypsum and ettringite. The
formation of thaumasite is of particular concern given the high level of carbonate in the system;
however there is often a precondition of low temperatures before this becomes a favourable
attack mechanism (Higgins and Crammond, 2003), although this is debatable (Irassar et al.,
2005). Nonetheless the chemical interactions involved in the production of gypsum, ettringite and
27
thaumasite, whether during a sulfate attack or during cement hydration, can be modified in the
presence of limestone. According to Gonzalez and Irassar (1998), during cement hydration
carbonate ions from the limestone filler compete with sulfate ions from gypsum to react with
aluminate ions from C3A forming monocarboaluminate, monosulfoaluminate and ettringite.
Irassar et al. (2003) detailed the sequence of a sulfate attack concluding that diffusion of sulfate
ions is followed by calcium hydroxide leaching, ettringite formation, gypsum formation and
depletion of CH. The latter stages involve the decalcification of C-S-H followed by thaumasite
formation.
The sequence of attack would corroborate well with what was noted in the experimental
results in section 4.2. As observed with CEM II/A-L limestone mix MA, there was an initial low
level expansion detected with very little visual deterioration which could indicate the onset of
ettringite or early gypsum formation. As the attack progressed white deposits began forming on
the exterior of each prism, followed by a lack of cohesion and spalling at the edges, possibly
indicating the decalcification of the C-S-H phase. Irassar et al. (2003) also describe corrosion of
edges and corners and attribute it to gypsum formation in parallel veins to the sulfate attack front.
As seen in Figure 4.4 cracks / veins with a white deposit can be observed at the elapsed exposure
time when the specimen began to shed mortar particles. Almost identical attack sequences were
observed in all mortar mixes undergoing observable degradation suggesting that none of these
phenomena are particularly unique to limestone cements. The CEM I specimens of MD however,
exhibited less visual evidence of white deposits and more physical effects in the form of
cracking, warping, spalling and surface delamination. This could perhaps be attributable to a
more dominant stage in the attack sequence compared to those observed in limestone cements.
In examining the results of the sulfate expansion experimental programme, it is clear that
the addition of a relatively high percentage of GGBS to both CEM I and CEM II mortars has had
a significant effect on their resistance to a 5% sodium sulfate solution. Both the CEM II mortars
(MB and MC) have shown the least amount of expansion and visual deterioration while the
CEMI I mortar with 70% GGBS (ME) has shown a resistance equalling SRPC for the majority of
the exposure period but eventually exceeding it. The sulfate resisting capabilities of GGBS have
been discussed on many occasions (BRE, 2003, Higgins and Crammond, 2003) with much of the
benefit being attributed to a denser matrix, decreased permeability and a reduction in calcium
hydroxide present in the hydrated system (Pava and Condren, 2008, Al-Dulaijan et al., 2003,
28
Osborne, 1999). Furthermore, with the formation of a secondary C-S-H phase attributable to the
interaction between calcium hydroxide and GGBS, much of the alumina in the system becomes
locked up in this product and is not available to form ettringite during a sulfate attack (Gollop
and Taylor, 1996). The authors also claim that as the percentage replacement of cement with
GGBS increases the proportion which reacts decreases with cement and this limits the quantity of
alumina released at high slag contents.
The combination of a reduction in calcium hydroxide, decreased permeability and the
locking up of potentially reactive alumina may account for the behaviour of the CEM I mortars
but it is essential to investigate any further effects of CEM II cements with a limestone addition.
The results presented above have indicated the potential increased benefit of using this with at
least 50% GGBS as a cement replacement. As previously discussed, limestone cements have an
absence of large capillaries which may delay the ingress of sulfates (Pipilikaki et al., 2009).
When combining this with the more impermeable matrix from GGBS cements, the opportunity
for sulfates to interact with the cement compounds is being severely limited. Visually, all
specimens containing GGBS have exhibited almost no evidence of a lack of cohesion from
exposure to the sulfate solution. Researchers (Brown and Taylor, 1999) have attempted to
account for this effect in limestone cements and have put forward a plausible explanation. With
an increase in GGBS levels, there is also an increase in hydrated C-S-H in the system.
Correspondingly, there is a decrease in the level of calcium hydroxide. Ettringite and gypsum
preferentially obtain their calcium from this phase but in the absence of a sufficient quantity
available, calcium from the C-S-H phase will serve as a source. This phase constitutes the
primary binding capability of a cement matrix and its degradation leads to a major loss in
cohesion. The authors claim that by adding calcium carbonate (limestone) as an additive, this in
turn will serve as the source of calcium for ettringite and gypsum thus preserving the integrity of
the C-S-H phase.
4.4
Sulfuric acid test results
4.4.1 Mass loss results

The measurement of a loss of mass of the concrete specimens was considered an acceptable
means of assessing the performance of each of the mixes in a sulfuric acid environment and was
29
previously used by Chang et al. (2005). The results of the first technique, using a wire brush, are
presented in Figure 4.11. The results of this procedure indicate that there may be a slight increase
in mass over the first twenty-eight days of exposure or very little mass loss. The concrete made
from CEM II-A/L limestone cement with no addition of GGBS showed a higher initial gain in
mass compared to the five other mixes, although the amount could be regarded as not significant.
After the initial month of exposure the decrease in mass remained constant for the most part with
little divergence from this trend. The performance of each of the six mixes remained largely
unchanged following completion of the testing programme, regardless of GGBS content or
cement type. Although the figures indicate that a 70% GGBS content, regardless of cement type,
performed the best throughout the testing period, the difference between the mix which
performed the worst (SRPC) was considered to be not significant. This is confirmation of the
aggressive nature of the sulfuric acid solution and the inherent difficulties in exposing
cementitious materials to this type of environment.
The graph in Figure 4.12 shows the results from exposure to the acid without using the
brushing technique. It can be seen that there is a slight increase in mass for all specimens within
the first twenty-eight days following which there is a steady increase in mass loss. This continues
at a similar rate until eighty-four days at which point there appears to be a small decrease in the
rate of mass loss for the unbrushed specimens compared with those that have been brushed at
weekly intervals. This point can be illustrated by Figure 4.13. The phenomenon appears to
coincide with the dissolution of the outer layer of the cement matrix and the protrusion of the
10mm and 20mm limestone aggregate although this apparent relationship does not seem
applicable to the brushed experiment.
30
Brushed Concrete
2000
Mass Loss (g/m^2)
0
-2000
56
112
168
CEM II 100%
CEM II + 50% GGBS
CEM II + 70% GBS
-4000
CEM I 100%
-6000
CEM I + 70% GGBS

-8000
SRPC
-10000
Days Exposure
Figure 4.11 Mass loss (brushed concrete)
Unbrushed Concrete
2000
Mass Loss (g/m^2)
0
-2000
56
112
168
CEM II 100%
CEM II + 50% GGBS
CEM II + 70% GBS
-4000
CEM I 100%
-6000
CEM I + 70% GGBS

-8000
-10000
SRPC
Days Exposure
Figure 4.12 Mass loss (unbrushed concrete)
31
CEM II 100%
2000
0
0
28
56
84
112
140
Mass Loss (g/m2)
Mass Loss (g/m2)
0
-2000
CEM II + 50% GGBS
2000
168
-4000
-6000
Unrbrushed
-8000
28
56
112
140
168
140
168
-6000
Unbrushed
-8000
Brushed
-10000
Days Exposure
84
-4000
Brushed
-10000
-2000
Days Exposure
.
(b)
CEM II + 70% GGBS
2000
CEM I 100%
2000
0
-2000
28
56
84
112
140
168
-4000
-6000
Unbrushed
-8000
Mass Loss (g/m2)
Mass Loss (g/m2)
28
84
Unbrushed
Brushed
Days Exposure
(c)
(d)
CEM I + 70% GGBS
SRPC 100%
2000
2000
0
0
28
56
84
112
140
Mass Loss (g/m2)
Mass Loss (g/m2)
0
-2000
112
-6000
-10000
Days Exposure
56
-4000
-8000
Brushed
-10000
-2000
168
-4000
-6000
Unbrushed
-8000
-2000 0
56
84
112
140
-4000
-6000
-8000
Brushed
28
Unbrushed
Brushed
-10000
-10000
Days Exposure
Days Exposure
(e)
(f)
Figure 4.13 (a-f) Comparison of brushed/un-brushed mass loss results
32
168
(a)
(d)
(b)
(e)
(c)
(f)
Figure 4.14 Typical corrosion levels for brushed concrete at 28, 56 & 84 days (a-c) and
unbrushed concrete over the same time intervals (d-f). Note differing degree of aggregate
exposure.
33
For both experiments there is very little between the performances of each of the six
different mixes in terms of mass loss or compressive strength. Although the data seems to suggest
that an addition of 70% GGBS improves the resistance to mass loss after six months, this must be
seen in the context of the compressive strength losing at least 60% of its 28-day value regardless
of the cement type or brushing technique used (Figure 4.17).
Several useful observations can be gleaned from the obtained data. It is clear that the use of
brushing to mimic abrasive behaviour (e.g. flowing water) has an effect on the loss of material
from the surface of concrete. (Figure 4.14 a-f). Allowing build-up to occur may slow down some
aspects of the corrosive effects of acid, albeit on a superficial basis, as clearly there are internal
chemical transformations occurring. This is again demonstrated by Figure 4.19 showing the
failure mechanism of a cube exposed to acid for six months. It is evident that a total loss of
cohesion has occurred throughout the specimen proving that while much of the ongoing reactions
are surface oriented there are more sinister forces at work beneath the cube surface. Furthermore,
there may be a useful relationship between the initial visibility of exposed aggregate and the
underlying state of the concrete integrity exposed to acidic environments as the cube strength
data reveals.
4.4.2 Discussion of deterioration mechanism

For both the brushed and unbrushed experimental programmes the primary mechanism of
deterioration was disintegration of the cement matrix along with some secondary spalling. There
was no evidence of cracking at any point over the six month exposure period. The manifestation
of the deterioration consisted of the formation on the surface of the cube specimens of a white
mushy substance (most likely gypsum) that was soft to touch and easy to remove. This was
visible after approximately one week of exposure to the acid and built up following each
successive removal of loosely adhering corrosion products. Regular examination of the
unbrushed concrete cubes also revealed the complete loss of cohesion of the surface layer of the
cement matrix after twelve weeks.
34
Figure 4.15 Complete surface delamination of one side of a 100mm cube exposed to 1%
sulfuric acid (unbrushed)
Figure 4.16 Concrete material losing cohesion and falling off the specimens
The type of deterioration visible showed the entire side of a cube fall away as a single piece
and this can be seen in the highlighted section of Figure 4.15. Regular examination of the brushed
35
specimens confirmed the mechanism of deterioration with material falling off the sides and
corners of the specimen and gathering at the bottom of the tank. This can be seen in Figure 4.16
and was a characteristic present throughout the duration of the experimental programme
(including that of the unbrushed specimens).
4.4.3 Cube strength tests

The experimental programme also examined the cube strengths of each of the mixes at twenty-
MA - 100% CEM II A/L
80
70
60
50
40
30
20
10
0
Cube strength (MPa)
Cube strength (MPa)
eight, fifty-six and one hundred and sixty eight days.
Cubes in water
Cubes in acid
28
56
84
112
Days
140
168
Cube strength (MPa)
Cube strength (MPa)
Cubes in water
Cubes in acid
28
56
84
112
Days
140
MB - CEM II A/L + 50% GGBS
Cubes in water
Cubes in acid
MC - CEM II A/L + 70% GGBS

80
70
60
50
40
30
20
10
0
80
70
60
50
40
30
20
10
0
168
56
84
Days
112
140
168
140
168
MD - 100% CEM I
80
70
60
50
40
30
20
10
0
Cubes in water
Cubes in acid
36
28
28
56
84
Days
112
SR - 100% SRPC
Cube Strength (Mpa)
Cube strength (MPa
ME - CEM I + 70% GGBS
80
70
60
50
40
30
20
10
0
Cubes in water
Cubes in acid
28
56
84
112
Days
140
80
70
60
50
40
30
20
10
0
168
Cubes in water
Cubes in acid
28
56
84
112
Days
140
168
Figure 4.17 Comparison between cube strength exposed to water only and 1% sulfuric acid
only (brushed)
4.4.4 Sulfuric acid expansion tests

Simultaneous to tests conducted on concrete cubes exposed to sulfuric acid, two prisms from
each mix were immersed in a 1% sulfuric acid solution while two were immersed in water over a
six-month period. The solution pH was kept at approximately 1.5 and refreshed at monthly
intervals where the acid was renewed and the containers cleaned of any debris. The change of
length of the prism from the initial reading is then calculated according to
Eqn. 1. The change in length of each of the specimens was measured
twice for accuracy and the results obtained are available in Appendix H.
The data showed that no appreciable expansion occurred and in fact minor contractions
were observed across all six mixes. The change in length of each of the specimens was measured
twice for accuracy, however it was found that at times there were differences between readings
from the same specimen, sometimes significant. It was concluded that the observed changes in
length may be due to experimental error and in fact relatively little movement was observed. The
procedure for measuring the specimens differed from those of the sulfate expansion tests in that a
metal ball had to be placed between the reference studs therefore minor deformities could not be
accounted for across the sphere. The reading on the comparator was also observed to vary
considerably while the specimen settled into the base groves. Again this behaviour was not
observed for the sulfate prism tests. According to Monteiro et al. (2008), an expansion of 0.5%
for concrete exposed to elevated sulfate levels was deemed as the failure point. As can be seen
37
from the experimental results, following six months of exposure to acid the movement in the
prisms was exceptionally far removed from this figure. The determination was that change of
length was not considered a significant contributor to concrete degradation when exposed to
sulfuric acid.
4.5
Ultrasonic results
4.5.1 Stiffness loss in due to sulfuric acid testing

The results in the previous section have shown the potential use for the application of ultrasonic
analysis of concrete, in conjunction with the shear wave detector algorithm developed by Bonal
et al. (2008), to monitor stiffness development in mixes containing varying percentages of
GGBS. In theory the same process has the potential to be used in recording the loss of stiffness in
concrete exposed to aggressive chemical environments. The technique is now applied to monitor
the degradation of 100mm cubes made with five concrete mixes with varying percentages of
GGBS, and one sulfate resisting SRPC mix, exposed to a 1% solution of sulfuric acid (H2SO4)
over a six month period. The cement type and percentage of GGBS used as a cement replacement
is indicated in the table below.
Table 4.3 Concrete mix designations for sulfuric acid tests

Mix Designation Cement Type % GGBS
MA
CEM II
MB
CEM II
50
MC
CEM II
70
MD
CEM I
ME
CEM I
70
SR
SRPC
Photographic observation of the cube specimens indicated the acid attack was primarily
focused on the cement matrix with the limestone aggregate largely avoiding the corrosive effects
38
(Figure 4.18). Failure of the specimen was by complete loss in cohesion of the binding properties
(Figure 4.19). The ultrasonic analysis therefore takes two approaches: monitoring the degradation
of concrete as a single inhomogeneous material and then again by considering it as a two-phase
model consisting of mortar and coarse aggregate. By doing this, it can be assumed that the cause
of a loss in stiffness in concrete is attributed to complete disintegration of the cement matrix
leaving the aggregate assumed to be unaffected by the acid.
Figure 4.18 Condition of a cube following six months exposure to sulfuric acid. The aggregate
remains largely unaffected while the cement matrix has suffered spalling and disintegration.
Figure 4.19 The same cube tested under compression until failure. The mode of failure clearly
indicates a loss of cohesion in the binding properties of the cement matrix.
39
In order to separate the concrete into a two

two-phase
phase system, a model was developed that
permits the velocity of an ultrasonic wave through concrete to be written in terms of the velocity
of the mortar component and the velocity of the coarse aggregate component (Lin et al., 2003).
2003)
Eqn. 2
Where C is the velocity in concrete, M is the velocity in mortar, CA is the velocity in coarse
aggregate, VM is the volume of mortar, VCA is the volume of coarse aggregate and VC is the
volume of concrete. By calculating the volume of coarse aggregate per 100mm cube specimen,
the phase was then considered as a single layer of limestone 46mm deep, the remaining 54mm
being the mortar phase. With volume parameters and the velocity of concrete known, using a
large specimen of limestone the ultrasonic velocities were also determined for the coarse
aggregate phase. The transmission of the signal through air voids and pores and the possible
Amplitude (micro-Volts)
effects of this were not considered.
Time (ns)
Figure 4.20 S-wave

wave signal from the solid limestone showing the first arrival point as
determined by the shear wave detector algorithm
Re-arranging
arranging the equation yields an expression for the velocity of an ultrasonic wave in
mortar, where CA is now the velocity through the solid limestone layer:
Eqn 3
40
4.5.2 Stiffness loss in concrete exposed to a 1% sulfuric acid solution

Ultrasonic testing was carried out on two samples stored in water and two samples stored in a 1%
sulfuric acid solution at twenty-eight day intervals for each of the six concrete mixes. The results
for those specimens made from CEM II-A/L with 0%, 50% and 70% GGBS used as a cement
replacement are presented in Figure 4.21, Figure 4.22 and Figure 4.23 respectively. It can be seen
that determining the small strain Youngs modulus using the shear wave detector algorithm has
the ability to monitor the degradation of concrete exposed to a 1% sulfuric acid solution. There is,
however, a difficulty in distinguishing between the six-month performances of each mix
individually, perhaps reflecting the aggressive nature of the solution in which they are stored.
Cubes containing both 50% and 70% GGBS, though, show a small resistance to a drop in the
small strain Youngs modulus up to approximately eighty-four days with the 70% GGBS
apparently showing almost complete resistance up to this point. This apparent beneficial
performance of GGBS may be somewhat misleading however, as the fifty-six day cube strengths
(for those exposed to acid) actually show a 46% drop (70% GGBS) and 42% (50% GGBS) drop
compared to those stored in water (Figure 4.17). The mix containing 0% GGBS showed the least
drop in strength recording a loss of only 30% in comparison. This brings up an interesting
possibility as to how GGBS may be affecting ultrasonic velocities in limestone concrete. As can
be seen from the results documenting early age strength gain, the small strain Youngs modulus
follows the trends of both the cube strengths and that of the static Youngs modulus much more
closely. At this early stage in hydration many of the chemical compounds giving concrete its
strength (and in particular GGBS concretes) have yet to be formed. The results also show that by
treating the concrete as a two-phase system, degradation of the mortar phase closely mimics the
trend of the system as a whole giving confidence in the fact that the disintegration of concrete can
be attributed to the loss in cohesion of the cement matrix.
41
Table 4.4 Sample data set obtained from the ultrasonic experimental programme. Values are
obtained up to week 24 for two samples stored in water and two stored in 1% sulfuric acid for
each time step.
Mix:
Calculation of Shear and Dynamic Modulus
MB
Week
Cube
TP-wave
VP-wave
TS-wave
VS-wave
Density
3
Poissons
(sec)
(m/sec)
(sec)
(m/sec)
(kg/m )
ratio
(GPa)
(GPa)
21.00
4975
31.0
3279
2400
0.116
25.8
58
12
20.40
5128
31.6
3215
2400
0.176
24.8
58
2400
2400
Ultrasonic Analysis (CEM II/A-L 100%)

70
Small Strain 'E' (Gpa)
60
50
40
30
20
Cubes in Water
Cubes in Acid
10
Mortar in Water
Mortar in Acid
0
0
28
56
84
112
140
168
Days Exposure to 1% Sulfuric Acid
Figure 4.21 Ultrasonic analysis of small strain Youngs modulus for mix MA immersed in 1%
sulfuric acid
42
Ultrasonic Analysis (CEM II/A-L + 50% GGBS)

70
60
50
40
30
20
Cubes in Water
Cubes in Acid
10
Mortar in Water
Mortar in acid
0
0
28
56
84
112
140
168
Figure 4.22 Ultrasonic analysis of small strain Youngs modulus for mix MB immersed in 1%
sulfuric acid
Ultrasonic Analysis (CEM II /A-L + 70% GGBS)

70
60
50
40
30
20
10
Cubes in Water
Cubes in Acid
Mortar in Water
Mortar in Acid
0
0
28
56
84
112
140
168
Figure 4.23 Ultrasonic analysis of small strain Youngs modulus for mix MC immersed in 1%
sulfuric acid
The results of the second set of three mixes detail the performance of CEM I with 0% and
70% GGBS as a cement replacement (Figure 4.24 and Figure 4.25). The performance of a
sulfate-resisting SRPC mix is also considered as a benchmark (Figure 4.26). Again it is clear that
the ultrasonic analysis has the ability to detect concrete degradation in the latter stages of the
43
experimental programme. The performance of the three mixes is somewhat ambiguous in the first
fifty-six days with little differences being recorded between those specimens stored in water and
those stored in acid. This again is somewhat misleading as the recorded cube strengths (see
Figure 4.17) begin to show a substantial loss in compressive resistance by this stage in the
programme. Furthermore, the ability to distinguish between the performance of a CEM I mix, a
CEM II-A/L mix and those containing GGBS is minimal. It is also clear that up to the time frame
between fifty-six days and eighty-four days it may be difficult for this method to detect any
degree of loss in stiffness.
The loss in concrete strength shown in Table 4.5 above indicates that regardless of the
cement type used the performance of each of the mixes after six months exposure to the acidic
solution is poor showing very little difference in the ability to resist the aggressive environment.
Given that the results of the ultrasonic tests also show few differences after six months, it could
be hypothesised that the method is indeed a reliable indicator in the latter stages of attack,
although seemingly less sensitive than the behaviour shown in the early age stiffness
development tests.
Table 4.5 Percentage loss in strength after six months exposure to a 1% sulfuric acid solution
Mix Designation
% loss in strength
MA
65%
MB
74%
MC
66%
MD
76%
ME
74%
SR
72%
44
Ultrasonic Analysis (CEM I 100%)

70
60
50
40
30
20
10
Cubes in Water
Cubes in Acid
Mortar in Water
Mortar in Acid
0
0
28
56
84
112
140
168
Figure 4.24 Ultrasonic analysis of small strain Youngs modulus for mix MD immersed in 1%
sulfuric acid
Ultrasonic Analysis (CEM I 70% GGBS)

70
60
50
40
30
20
10
Morar in Water
Cubes in Water
Cubes in Acid
Mortar in Acid
0
0
28
56
84
112
140
168
Figure 4.25 Ultrasonic analysis of small strain Youngs modulus for mix ME immersed in 1%
sulfuric acid
45
Ultrasonic Analysis (SRPC 100%)

70
60
50
40
30
20
Mortar in Water
Cubes in Water
10
Cubes in Acid
Mortar in Acid
0
0
28
56
84
112
140
168
Days Expsoure to 1% Sulfuric Acid
Figure 4.26 Ultrasonic analysis of small strain Youngs modulus for mix SR immersed in 1%
sulfuric acid
4.5.3 Discussion of ultrasonic results

There remains a distinct lack of in-depth knowledge into the relationship between ultrasonic
velocities and the development or degradation of stiffness in concrete. Much of the discussion
centres around two aspects of concrete: the microstructural make-up of the mix and the influence
of hydration products (and consequently corrosion products). The ultrasonic results presented
show that the shear wave detector algorithm appears to be more sensitive to a change in stiffness
in the early days of hydration but less so when monitoring the effects of corrosion due to sulfuric
acid attack. To account for these differences it is essential to outline the factors affecting both
processes.
4.5.4 Microstructural Effects

Three parameters within the microstructural make-up of a concrete mix have been attributed to
variations in ultrasonic pulse velocities: entrapped air voids, the water/cement ratio and the
arrangement of aggregate in the mix. For concrete in the early stages of hydration it has been
shown that the velocity of p-waves are slow to develop (Robeyst et al., 2008) but, as can be seen
from the results achieved in the early age tests in section 4.4.1, this begins to approach an
asymptotic value after a few days of hydration for both P-waves and S-waves.
46
5500
5000
Velocity (m/s)
4500
P-wave velocity
4000
S-wave velocity
3500
3000
2500
2000
0
10
15
20
25
Time (Days)
Figure 4.27 Development of P-wave and S-wave velocities in early age stiffness development
Robeyst et al. (2008) showed that it was in the first twenty-four hours that the greatest gain
in P-wave velocity was observed. With regard to the ultrasonic tests carried out on specimens
exposed to sulfuric acid, there was almost no effect on the P-wave velocity over the six-month
experimental period with it generally remaining at a consistent level for all mixes. This is
interesting as it has been claimed that P-wave velocity is directly related to the dynamic Youngs
modulus (Voigt et al., 2005). Clearly however, the observed drop in cube strengths (Figure 4.17)
show that the stiffness decreased over the exposure period. This would seem to indicate that Pwave velocities may solely be an indicator of cement particle interconnectivity and not
necessarily of stiffness (i.e. there may be bonds but they might be weak). In a hydrating mix, for
instance, cement particles remain in suspension for a period and the wave paths thus remain
elongated due to the presence of entrapped air voids (Lee et al., 2004, Chaix et al., 2006, Robeyst
et al., 2008), thus increasing the time from transmitter to receiver. With regard to a specimen
degrading from exposure to sulfuric acid, the cement particles are not in a fluidic suspension and
remain bonded, although perhaps with increasing weakness as time progresses. It may also be
hypothesised that the corrosion products formed in the acid attack (e.g. gypsum) may fill the air
voids providing an unobstructed wave path and masking the effects of a loss of stiffness on Pwave velocities. This type of behaviour occurs during hydration when primary ettringite serves as
a medium through which p-waves can travel, giving a false indication of stiffness development.
47
The effect of the water to cement ratio also has a bearing on the velocity of ultrasonic
waves in concrete. Although for this experimental programme the value was constant at 0.45, it is
still worthwhile to mention the effect it has on the cementitious system. According to one group
of authors, for concrete with a w/c ratio greater than 0.5 an increase in aggregate content will lead
to an increase in ultrasonic velocity but with little increase in strength. Conversely, for a high w/c
ratio an increase in cement content will lead to a decrease in ultrasonic velocity while for a low
w/c ratio the velocity doesnt change as the cement matrix is already dense. The increase in w/c
ratio effectively increases the distance between cement particles, complicating wave transmission
by the non-direct path from transmitter to receiver while the degree of tortuosity of the paste also
has a similar effect (Lee et al., 2004). Furthermore as concrete is not a homogeneous material, it
cannot be said with certainty how the transmission of waves through aggregate-paste boundaries
affects the received signal.
While the influence of air voids and the interconnectivity of cement particles obviously
affect ultrasonic velocities, this merely takes into account the microscopic variabilites. Those
particles on a much larger scale, however, cannot be ignored. The internal settling of aggregate
leads to an increase in ultrasonic velocity while the downward movement during compaction
must also be taken into account. Lin et al (2003) also point out that the distribution of aggregate
within a specimen may have an unexpected effect on the ultrasonic velocity. If the aggregate is
concentrated along the direct line from the ultrasonic transducer transmitting the signal to the
receiver then naturally the wave will travel through more aggregate and the velocity of the wave
will be high. However, if the aggregate is sparse around this line then the velocity will be
comparatively low. This may be an issue for laboratory prepared concrete due to individual
compaction techniques and could differ from that found on site.
4.5.5 Chemical effects

The lack of a substantial difference in performance of concrete exposed to sulfuric acid means it
is quite difficult to pinpoint any effects rising from the presence of limestone in the cement or
indeed that of GGBS. As a result much of what can be discussed arises from the early age tests
but nonetheless may contribute to the performance of the sulfuric acid programme. Both the
formation of primary ettringite during hydration and the effect of the CSH phase subsequently
48
have been found to contribute to variations in ultrasonic velocities. Concretes made with GGBS
form a greater degree of CSH due to the interaction between the former and hydrated calcium
hydroxide. The resulting linkages between cement grains and aggregates provide a path for wave
propagation increasing the velocity. The CSH phase is the main binding compound in concrete
but in concretes made with GGBS this takes time to develop. In early ages tests the 70% GGBS
mix showed the slow development of both velocity and small strain stiffness reflecting the lack
of appreciable CSH formed. After the cubes are immersed in sulfuric acid, the effect may not be
so clear. Both mixes with 70% GGBS (MC and ME) show an early reluctance to a decrease in
small strain stiffness up to eighty-four days, thereafter however, the trend is downward. The
mixes without GGBS (MA and MD) show a drop in small strain Youngs modulus relative to an
initial value. However the final result for all mixes is rather uniform possibly reflecting the
aggressiveness of the environment.
With regard to ettringite formation, this may be more applicable to the early age tests.
Ettringite is unstable in pH values below approximately 11 after which it decomposes. The
sulfuric acid tests are carried out in a solution that has a pH of approximately 1.5 and it could be
assumed that the presence of ettringite is neglected when assessing the ultrasonic results of
concrete in this environment. Nevertheless it has been pointed out that the formation of primary
ettringite during hydration contributes to an increase in p-wave velocity but this has no bearing
on the strength or stiffness of concrete. The ettringite needles fill the pore space previously
occupied by water with a solid product decreasing the space filled with air voids and allowing the
transmission of ultrasonic waves. It could be hypothesised that when concrete is attacked by the
sulfuric acid, forming gypsum and filling the voids of the surrounding spaces, the same behaviour
may occur and affect an accurate assessment of the materials stiffness.
4.6 Permeability, absorption and sorptivity results

The following table presents the results from the experimental programme.
49
Table 4.6 Permeability and absorption results

Mix
Air permeability
2
(ln(m )/s)
Water permeability
3
Absorption
0.5
(m3/min)
(m /min )
Sample a
Sample b
Sample a
Sample b
Sample a
Sample b
MA
-0.054
-0.028
3.87E-08
1.78E-08
1.56E-08
2.27E-08
MB
-0.047
-0.013
2.35E-08
1.30E-08
5.07E-09
4.04E-09
MC
-0.055
-0.018
3.12E-08
1.96E-08
2.59E-08
1.59E-08
MD
-0.073
-0.015
7.57E-08
2.68E-08
3.97E-08
1.45E-08
ME
-0.034
-0.014
4.07E-08
2.15E-08
2.44E-08
2.56E-08
SR
-0.082
-0.006
6.44E-08
2.25E-08
5.35E-08
1.70E-08
The goal of the permeability and sorption testing was to ascertain a performance ranking of the
six concrete mixes. The results of the investigation proved somewhat inconclusive with obtained
values at times differing significantly for identical mix specifications. The results may be due to
experimental error, as the Autoclam requires a completely sealed testing surface, or due to the
effect that aggregate has on the diffusion characteristics of the concrete.
50
5 DISCUSSION
5.1 Sulfate experimental programme
While it has been stated that testing through sulfate exposure to assess concrete tolerance to
wastewater applications is largely an inaccurate method (Monteny et al., 2000), it is clear that this
particularly important fact has not been accepted or realised within the engineering community.
The sulfate testing procedure in this experimental programme was designed to highlight any
variations in the performance of CEMI I, CEM II-A/L and various combinations of GGBS when
compared to SRPC, the standard specification cement for wastewater applications. The results of
the investigation highlighted some very significant differences in the attack mechanism compared
with results obtained in sulfuric acid exposure tests and the conditions observed in two
wastewater treatment plants at Swords in North Co. Dublin and Kilkenny in the midlands. While
the condition of the concrete in both plants resembled the effects of the acid tests the sulfate
testing programme yielded starkly differing results.
Several significant behavioural differences were monitored over the course of the
investigation; while the specimens submersed in a 50g/l sodium sulfate solution exhibited
expansion, cracking and warping those in acid showed only mass loss and disintegration of the
cement matrix. The manifestation of attack also progressed at different paces. While the prisms in
the accelerated sulfate tests took several weeks, sometimes months, to show appreciable
expansion or appearance of corrosion products (other than the CEM I 100% specimens), the
cubes submersed in the 1% sulfuric acid solution began to deteriorate within days. These cubes
rapidly began to show build-up of a white mushy material followed then by mass loss. This
clearly shows that exposure to sulfuric acid is a more aggressive form of attack and may result in
substantially decreased service life estimates. The sulfate tests also demonstrated the ability to
significantly distinguish between the performances of CEM I, CEM II-A/L, SRPC and various
additions of GGBS. Throughout the experimental programme the cement paste of each prism
largely remained intact. Minimal build up of any corrosion products was observed and only the
extreme corners of the specimens showed any mass loss. These behavioural differences call into
question the differences in the chemical makeup of both the solutions used. While each contains a
sulfate ion, traditionally considered the main aggressor, the presence of a H+ ion from the sulfuric
acid solution is clearly having the most detrimental effect resulting in a lack of cohesion and an
51
effective dissolution of the cement matrix. With regard to the sulfate testing procedures, further
investigations into the mechanism of attack may be investigated by modifying the solution by
using magnesium sulfate for example. Research has suggested that this attacks primarily the CSH
phase of cement rather than calcium hydroxide in order to obtain the calcium used in its
degradation process. It is unclear whether this may be a more beneficial test to conduct in
conjunction with sulfuric acid tests; however sodium sulfate has generally been recognised as the
standardised solution for sulfate exposure and is used by both the ASTM C1012 and the Dutch
CUR 48 tests.
It can be concluded that in the context of concrete in wastewater applications, standard tests
to investigate the sulfate performance of a variety of mixes cannot be considered as a reliable
indicator for representing in-service conditions.
The tests carried out in this experimental
investigation, however, have highlighted the necessity to affect a change in practice when
specifying concrete for aggressive wastewater applications. The stark contrast in both the
manifestation of corrosion and the physical effects on the cementitious system serve as proof that
this is an urgent requirement that needs to be accounted for. Whats most alarming, however, is
that there appears to be an inability for any concrete to survive this acidic environment despite
the mix being designed to EN 206 XA3 class, deemed the most resistant specification against
chemical attack. It should be noted however that the test solution of pH 1.5 represents the most
severe conditions to be expected in service. The pH may vary in reality on account of
environmental conditions, including temperature and humidity, which undoubtedly affect the
activity of the sulfuric acid producing bacteria. Sulfate tests may draw a concrete specifier into a
false sense of security and while this may satisfy the requirements of current standards, it is clear
that it does not satisfy the true nature of the problem.
5.2 Sulfuric acid programme

A search of existing literature yielded a general consensus that an appropriate procedure for
mimicking the aggressive conditions present in wastewater treatment systems was through the
exposure of concrete to a 1% solution of sulfuric acid (H2SO4) (Chang et al., 2005, Monteny et
al., 2000). The results from this experimental procedure showed that after six months of
exposure, the cubes (which were regularly brushed) lost at least 65% of their strength. Chang et
52
al. (2005) showed reductions in strength not exceeding 30% for five out of six cases over an
identical time period and using a similar experimental regime, although only two of those were
mixes similar to this programme. A contributing factor toward the authors result however may
be to what extent the specimens are brushed. Chang et al. (2005) recorded rinsing the specimens
under flowing water and gently brushing them of loose material with a wire brush. The brushing
conducted in this investigation varied from extensive removal of loose material with regular wire
brushing and then again using only flowing tap water to rid the cube of excess build-up. A small
decrease in the rate of mass loss was noted after eighty-four days using the rinsing method
although the differences may be regarded as not significant. The extent of brushing was an
important part of the regime as the idea was to create conditions representative of the bacterial
environment detailed in the literature review. It is unclear whether the assumption of a 1%
sulfuric acid solution is representative of the in-service conditions but it may, however, constitute
an acceptable component in an accelerated test method. The effect of various brushing techniques
yields results that are also far from conclusive and may confirm the suspected intolerance of
concrete to aggressive sulfuric acid environments regardless of the effects of abrasion.
The acid testing programme also raised concerns over the use of sulfate resisting Portland
cement in wastewater applications. It now appears there is a common misconception that
specifying a SRPC mix will sufficiently resist the expected aggressive sulfate environment.
While this is not entirely untrue (some industries such as the brewing industry discharge sulfateladen waters from their production processes), it is clear that some form of extra protection is
required for these treatment systems to adequately resist the acidic conditions over a long period
of time. The results presented in this investigation show almost no benefit in using GGBS.
Despite the reduced amount of calcium hydroxide (and the resulting lesser quantities of gypsum
formed as a result of sulfuric acid attack), this does not account for any improvements in the
performance of GGBS concrete. This calls into question other factors such as the possible
increased capillary effect of the GGBS mixes, from decreased pore sizes, or more likely the
dissolution effect of the hydrogen ion of the sulfuric acid. The results from the sulfate prism tests
further highlight the differences in attack mechanisms despite many of the same corrosion
products (i.e. gypsum) being present in both instances.
The sulfuric acid tests in this investigation, while highlighting the vulnerabilities to acidic
conditions, suffer from some inaccuracies inherent in accelerated testing. As has been mentioned,
53
the attack present in wastewater systems is bacterial in nature (not purely chemical), evolving
over a period of time far exceeding the six months used in this investigation. Environmental
conditions also play a role; in-service infrastructure will experience temperature fluctuations from
night to day and from season to season. Water levels may also rise and fall in reality, creating
wetting and drying conditions which are known to be more detrimental to concrete corosion.
When this is combined with varying water flows, the experimental programme cannot claim to
represent each and every environmental condition that will be present over the service life of a
component. It can however, serve as an indicator in the performance of various concrete mixes
to this highly aggressive environment. While more accurate methods exist of replicating the
bacterial environment, the complexity of such an investigation is both time consuming and cost
prohibitive. The experimental programme carried out in this instance may therefore represent the
most accurate method available at minimal cost with the least constraints on time.
5.3 Ultrasonic analysis

The results obtained from the laboratory results have shown the potential for assessing the small
strain Youngs modulus of concrete. It is not clear however to what extent the technique may be
useful as the results from the early age programme and sulfuric acid deterioration tests show
small strain stiffness profiles which vary in sensitivity between test programmes. The latter tests
appear to struggle initially to register a drop in stiffness, as evidenced by concurrent cube
strengths, indicating that using the current technique in practice may not adequately reflect the
integrity of the concrete until it has entered an advanced deterioration stage. Furthermore the
practicalities of the actual test may also pose difficulties. The method relies on through
transmission requiring both a transmitter and receiver at either side of the concrete and while
this is achievable in a laboratory environment with 100mm cubes, positioning ultrasonic
transducers in a service environment may also pose difficulties. The method also does not take
into account the presence of steel reinforcement likely to be found in concrete wastewater
treatment plant structures further adding to the heterogeneous nature of concrete and
complicating the technique.
The shear wave detector method demonstrated potential in advancing ultrasonic nondestructive techniques for concrete. The results showed it was possible to plot the development of
54
small strain stiffness in concrete at early ages and distinguish between the different binders used.
The method appeared less accurate however, in monitoring a loss in stiffness following exposure
to a 1% sulfuric acid solution for six months. At the same it was less clear to distinguish between
the different binders used which may possibly reflect the very harsh nature of the aggressive
solution to calcium-based cementitious materials.
55
6 CONCLUSIONS
The most important aspect of this research has been highlighting the significant differences
between sulfate attack and sulfuric acid attack. Based on the obtained data the former is clearly
an expansion dominated phenomenon with a defined point of corrosion acceleration. The latter,
however, appears to be a surface dissolution mechanism combined with an extremely destructive
/ rapid diffusion process that immediately leads to an attack on the binding capabilities of cement
This has implications with respect to the fact that current design specifications for water and
wastewater treatment facilities call for the widespread use of sulfate-resisting cement,. The
specifications fail to account for the presence of an extremely corrosive acidic environment that
can ultimately affect whole-life costs.
Furthermore, the current European EN206 standards also fail to account for pH
environments below 4 which literature has suggested is far higher than what is commonly
encountered in wastewater facilities. It has already been highlighted that there is a noticeable
change between pH 4 and pH 1 in terms of mass loss acceleration, indicating an increase in the
severity of attack.
6.1 Sodium sulfate tests

The sodium sulfate expansion tests highlighted some of the key differences between the expected
and actual deterioration mechanisms in a wastewater treatment environment. Similarities are also
noted. The experimental programme also recorded an apparent relationship between expansion
and the square-root of time with each stage characterised by a specific physical deterioration
mechanism. The main conclusions that can be drawn are thus:
Deterioration was primarily due to bulging, spalling and warping, most likely as a result
of the formation of gypsum. This type of mechanical deterioration is not generally
expected in a wastewater environment.
Some softening of the interior of the matrix along with a white substance confirmed this
as the most likely case. The presence of gypsum is more than likely to occur in
conjunction with biogenic sulfuric acid corrosion, unless the material is washed away.
This may cause confusion as to the nature of the attack.
Specimens containing GGBS outperformed all other mixes regardless of the cement type.
56
CEM II/A-L limestone cements appear to possess and inherent sulfate resisting capability
that is superior to a CEM I cement. When combined with 50% or 70% GGBS it
represented the best performing binder combination.
100% CEM I was the worst performing cement
All conclusions are based on findings from exposing mortar prisms to the aggressive solution.
The behaviour of concrete may differ from those observed in the mortar tests.
6.2 Sulfuric acid tests

The sulfuric acid test programme primarily indicated the inability of concrete to survive very
aggressive sulfuric acid solutions. Furthermore, a collaboration of existing data of acidic
corrosion shows that this may apply to a large variety of acids including acetic and lactic acids.
The findings show that solution pH may be a controlling force in the deterioration process. The
test programme again served to highlight both the significant differences and slight similarities
between sulfate and sulfuric acid based deterioration mechanisms. The main conclusions that can
be drawn are thus:
Sulfuric acid deterioration visually appeared to be more surface oriented than sulfate
attack. The attack was concentrated primarily on the matrix of the cement.
The main deterioration mechanism consisted of the formation of gypsum on the external
surfaces of the concrete specimens. This was followed by surface delamination, some
spalling. In the long term a widespread lack of cohesion leads to a failure mechanism that
spreads directly to the core.
With reference to mass loss, there was very little distinction between the performances of
each of the six mixes. Some minor differences were, however, noted. An initial increase
(or no decrease) in mass for the first 28 days appeared to be common to all mixes and test
conditions.
The use of brushing appeared to increase the rate of attack and the level of mass loss at
six months by a factor of approximately 1.5. It is unclear to what extent the use of
brushing replicates actual corrosion mechanisms.
57
Mass loss may not be an accurate performance indicator of the deterioration level. Despite
a difference between the brushed and unbrushed specimens, cube strengths revealed
almost no change in performance.
Expansion was not deemed to be an important parameter in sulfuric acid based

degradation.
The use of GGBS appeared to have little or no effect on improving resistance. Similarly
SRPC had no effect on the performance of concrete in this environment.
The rate of visual deterioration of a 1% solution of sulfuric acid attack greatly exceeded
that of a 5% sodium sulfate solution.
The 1% sulfuric acid solution (pH1.5) represents the most severe conditions to be
expected in service. Actual pH levels may vary according to time, temperature and
bacterial activity.
Sulfate deterioration differs from that of sulfuric acid deterioration. It may be possible
upon visual examination to confuse the two mechanisms on account of the presence of
gypsum, common to both.
6.3 Summary
The results of this investigation have clearly outlined the cause of concrete deterioration in
wastewater treatment systems. Consequently, a clear distinction has been drawn between
degradation due to sulfate attack and that due to a sulfuric acid attack in this environment. It is
evident that neither the concrete standards nor concrete specifiers are taking into account the
harsh nature of this form of attack by suitably distinguishing between the two corrosion
phenomena. The laboratory programme has also failed to highlight a concrete specification that is
capable of withstanding biodeterioration. For this to be fully addressed, the range of aggressive
environments associated with wastewater applications needs to be quantified and used as an input
for future research work.
58
REFERENCES
AL-DULAIJAN, S. U., MASLEHUDDIN, M., AL-ZAHRANI, M. M., SHARIF, A. M.,
SHAMEEM, M. & IBRAHIM, M. (2003) Sulfate resistance of plain and blended cements
exposed to varying concentrations of sodium sulfate. Cement and Concrete Composites, 25, 429437.
ASTM (2004) C1012 - 04 Standard Test Method for Length Change of Hydraulic-Cement
Mortars Exposed to a Sulfate Solution.
BONAL, J., DONOHUE, S. & MCNALLY, C. (2008) Examination of a novel wavelet approach
for bender element testing. In: CANNON, E., WEST, R. & FANNING, P eds. Bridge and
Infrastructure Research in Ireland, BRI 2008 Galway, Ireland, 4-5 December.
BONAL, J., DONOHUE, S. & MCNALLY, C. (2010) Wavelet analysis of bender element
signals, Geotechnique, submitted for publication.
BONAVETTI, V. L., RAHHAL, V. F. & IRASSAR, E. F. (2001) Studies on the carbo-aluminate
formation in limestone filler-blended cements. Cement and Concrete Research, 31, 853-859.
BRE (2003) BRE Special Digest 1, Concrete in Aggressive Ground. Part 1: Assessing the
aggressive chemical environment. 2nd Edition ed. Watford, England.
BROWN, P. W. & TAYLOR, H. F. W. (1999) The role of ettringite in external sulfate attack. In:
MARCHAND, J. & SKALNY, J. (Eds.) Proceedings of Seminar on sulfate attack mechanisms.
Quebec, Canada.
CHAIX, J.-F., GARNIER, V. & CORNELOUP, G. (2006) Ultrasonic wave propagation in
heterogeneous solid media: Theoretical analysis and experimental validation. Ultrasonics, 44,
200-210.
CHANG, Z.-T., SONG, X.-J., MUNN, R. & MAROSSZEKY, M. (2005) Using limestone
aggregates and different cements for enhancing resistance of concrete to sulfuric acid attack.
Cement and Concrete Research, 35, 1486-1494.
GOLLOP, R. S. & TAYLOR, H. F. W. (1996) Microstructural and microanalytical studies of
sulfate attack. V. Comparison of different slag blends. Cement and Concrete Research, 26, 10291044.
GONZLEZ, M. A. & IRASSAR, E. F. (1998) Effect of limestone filler on the sulfate resistance
of low C3A portland cement. Cement and Concrete Research, 28, 1655-1667.
HEKAL, E. E., KISHAR, E. & MOSTAFA, H. (2002) Magnesium sulfate attack on hardened
blended cement pastes under different circumstances. Cement and Concrete Research, 32, 14211427.
HIGGINS, D. D. & CRAMMOND, N. J. (2003) Resistance of concrete containing ggbs to the
thaumasite form of sulfate attack. Cement and Concrete Composites, 25, 921-929.
HOOTON, R. D. (1990) Effects of carbonate additions on heat of hydration and sulfate resistance
of Portland cements. IN: KLIEGER, P. & HOOTON, R.D. (Eds) Carbonate Additions to Cement,
ASTM Special Technical Publication.
59
HORNAIN, H., MARCHAND, J., DUHOT, V. & MORANVILLE-REGOURD, M. (1995)

Diffusion of chloride ions in limestone filler blended cement pastes and mortars. Cement and
Concrete Research, 25, 1667-1678.
IRASSAR, E. F., BONAVETTI, V. L. & GONZLEZ, M. (2003) Microstructural study of
sulfate attack on ordinary and limestone Portland cements at ambient temperature. Cement and
Concrete Research, 33, 31-41.
IRASSAR, E. F., BONAVETTI, V. L., TREZZA, M. A. & GONZLEZ, M. A. (2005)
Thaumasite formation in limestone filler cements exposed to sodium sulphate solution at 20 C.
Cement and Concrete Composites, 27, 77-84.
IRASSAR, E. F., GONZLEZ, M. & RAHHAL, V. (2000) Sulphate resistance of type V
cements with limestone filler and natural pozzolana. Cement and Concrete Composites, 22, 361368.
LEE, H. K., LEE, K. M., KIM, Y. H., YIM, H. & BAE, D. B. (2004) Ultrasonic in-situ
monitoring of setting process of high-performance concrete. Cement and Concrete Research, 34,
631-640.
MONTEIRO, P. J. M. & KURTIS, K. E. (2008) Experimental Asymptotic Analysis of Expansion
of Concrete Exposed to Sulfate Attack. ACI Materials Journal, 105, 62-71.
NEVILLE, A. (1995) Properties of Concrete, Harlow, England, Longman.
O'CONNELL, M., MCNALLY, C. & RICHARDSON, M.G. (2010) 'Biochemical attack on
concrete in wastewater applications: a state of the art review'. Cement and Concrete Composites,
32, 479-485
O'CONNELL, M., MCNALLY, C., DONOHUE, S. & RICHARDSON, M.G. (2009) Assessment
of ultrasonic signals to determine the early age properties of concretes incorporating secondary
cementitious materials. In: Proceedings of the 15th European Meeting of Environmental and
Engineering Geophysics, Dublin, 7- 9 September.
OSBORNE, G. J. (1999) Durability of Portland blast-furnace slag cement concrete. Cement and
Concrete Composites, 21, 11-21.
PAVA, S. & CONDREN, E. (2008) Study of the Durability of OPC versus GGBS Concrete on
Exposure to Silage Effluent. Journal of Materials in Civil Engineering, 20, 313-320.
PIPILIKAKI, P., KATSIOTI, M. & GALLIAS, J. L. (2009) Performance of limestone cement
mortars in a high sulfates environment. Construction and Building Materials, 23, 1042-1049.
RAMEZANIANPOUR, A. A., GHIASVAND, E., NICKSERESHT, I., MAHDIKHANI, M. &
MOODI, F. (2009) Influence of various amounts of limestone powder on performance of
Portland limestone cement concretes. Cement and Concrete Composites, 31, 715-720.
RAMYAR, K. & INAN, G. (2007) Sodium sulfate attack on plain and blended cements. Building
and Environment, 42, 1368-1372.
ROBEYST, N., GRUYAERT, E., GROSSE, C. U. & DE BELIE, N. (2008) Monitoring the
setting of concrete containing blast-furnace slag by measuring the ultrasonic p-wave velocity.
Cement and Concrete Research, 38, 1169-1176.
60
TIAN, B. & COHEN, M. D. (2000) Does gypsum formation during sulfate attack on concrete
lead to expansion? Cement and Concrete Research, 30, 117-123.
TOSUN, K., FELEKOGLU, B., BARADAN, B. & AKIN ALTUN, I. (2009) Effects of
limestone replacement ratio on the sulfate resistance of Portland limestone cement mortars
exposed to extraordinary high sulfate concentrations. Construction and Building Materials, 23,
2534-2544.
TSIVILIS, S., TSANTILAS, J., KAKALI, G., CHANIOTAKIS, E. & SAKELLARIOU, A.
(2003) The permeability of Portland limestone cement concrete. Cement and Concrete Research,
33, 1465-1471.
VOIGT, T., GROSSE, C. U., SUN, Z., SHAH, S. P. & REINHARDT, H. W. (2005) Comparison
of ultrasonic wave transmission and reflection measurements with P-and S-waves on early age
mortar and concrete. Materials and Structures, 38, 729-738.
61
APPENDIX A: Review Paper
APPENDIX C: Sodium Sulfate Expansion Data

CEM II-A/L 100%
0.3
Expansion %
0.25
0.2
Prism 1
0.15
Prism 2
0.1
Prism 3
Prism 4
0.05
0
0
56
112
168
224
280
336
392
448
504
560
Days Exposure
Days
0
28
56
84
112
140
175
196
224
252
280
308
336
364
392
420
448
476
504
L (%) P1
0
0
0.006
0.012
0.025
0.027
0.029
0.035
0.043
0.045
0.051
0.06
0.066
0.073
0.081
0.101
0.105
0.119
0.141
L (%)P2
0.000
0.000
0.003
0.007
0.018
0.031
0.029
0.034
0.046
0.053
0.062
0.077
0.090
0.109
0.128
0.154
0.182
0.222
0.268
L (%)P3
0
0.01
0.004
0.01
0.019
0.024
0.026
0.031
0.041
0.046
0.045
0.053
0.058
0.069
0.077
0.093
0.102
0.119
0.138
L (%)P4
0
0.01
0.01
0.016
0.027
0.029
0.031
0.037
0.046
0.047
0.05
0.058
0.062
0.072
0.078
0.092
0.097
0.114
0.131
CEM II-A/L + 50% GGBS

0.04
0.035
Expansion %
0.03
0.025
Prism 1
0.02
Prism 2
0.015
Prism 3
0.01
Prism 4
0.005
0
0
56
112
168
224
280
336
392
448
504
560
Days Exposure
Days
0
28
56
84
112
140
175
196
224
252
280
308
336
364
392
420
448
476
504
L (%)P1
0
0.004
0.006
0.012
0.019
0.015
0.013
0.015
0.017
0.018
0.017
0.018
0.018
0.018
0.021
0.021
0.022
0.026
0.027
L (%)P2
0.000
0.006
0.007
0.012
0.018
0.018
0.016
0.017
0.017
0.020
0.022
0.022
0.024
0.024
0.026
0.028
0.030
0.030
0.032
L (%)P3
0
0.004
0.008
0.009
0.013
0.016
0.015
0.016
0.017
0.017
0.020
0.021
0.022
0.022
0.026
0.025
0.027
0.030
0.030
L (%)P4
0
0.006
0.005
0.011
0.012
0.015
0.019
0.018
0.020
0.021
0.024
0.026
0.026
0.027
0.03
0.031
0.032
0.033
0.035
CEMII-A/L + 70% GGBS

0.04
0.035
Expansion %
0.03
0.025
Prism 1
0.02
Prism 2
0.015
Prism 3
0.01
Prism 4
0.005
0
0
56
112
168
224
280
336
392
448
504
560
Days Exposure
Days
0
28
56
84
112
140
175
196
224
252
280
308
336
364
392
420
448
476
504
L (%)P1
0
0.005
0.004
0.008
0.010
0.013
0.017
0.02
0.019
0.022
0.024
0.026
0.026
0.026
0.029
0.028
0.034
0.033
0.033
L (%)P2
0.000
0.002
0.004
0.010
0.010
0.015
0.012
0.014
0.014
0.017
0.018
0.021
0.020
0.021
0.024
0.026
0.030
0.030
0.031
L (%)P3
0
0.008
0.002
0.012
0.014
0.016
0.015
0.017
0.017
0.020
0.022
0.023
0.023
0.024
0.027
0.027
0.029
0.031
0.035
L (%)P4
0
0.005
0.004
0.012
0.010
0.014
0.014
0.016
0.017
0.019
0.02
0.025
0.023
0.024
0.029
0.027
0.03
0.032
0.036
CEM I 100%
0.8
0.7
Expansion %
0.6
0.5
Prism 1
0.4
Prism 2
0.3
Prism 3
0.2
Prism 4
0.1
0
0
56
112
168
224
280
336
392
448
504
Days Exposure
Days
0
28
56
84
119
140
168
196
224
252
280
308
336
364
392
420
448
L (%)P1
0
0.013
0.025
0.029
0.037
0.048
0.059
0.072
0.088
0.109
0.123
0.153
0.185
0.249
0.309
0.407
0.546
L (%)P2
0.000
0.003
0.015
0.024
0.031
0.043
0.055
0.068
0.084
0.104
0.122
0.153
0.184
0.239
0.297
0.377
0.502
L (%)P3
0
0.008
0.022
0.031
0.041
0.056
0.071
0.086
0.107
0.134
0.162
0.209
0.258
0.341
0.445
0.571
0.725
L (%)P4
0
0.014
0.026
0.034
0.046
0.058
0.072
0.089
0.109
0.132
0.155
0.196
0.236
0.315
0.404
0.52
0.664
CEM I + 70% GGBS

0.06
Expansion %
0.05
0.04
Prism 1
0.03
Prism 2
0.02
Prism 3
Prism 4
0.01
0
0
56
112
168
224
280
336
392
448
504
Days Exposure
Days
0
28
56
84
119
140
168
196
224
252
280
308
336
364
392
420
448
L (%)P1
0
0.003
0.006
0.015
0.013
0.018
0.016
0.019
0.02
0.021
0.023
0.023
0.024
0.028
0.03
0.031
0.033
L (%)P2
0.000
0.008
0.012
0.016
0.017
0.021
0.024
0.026
0.028
0.033
0.034
0.034
0.039
0.041
0.042
0.046
0.049
L (%)P3
0
0
0.006
0.009
0.014
0.017
0.018
0.021
0.023
0.025
0.026
0.028
0.029
0.034
0.034
0.035
0.037
L (%)P4
0
0.002
0.008
0.013
0.021
0.024
0.026
0.028
0.031
0.034
0.036
0.038
0.039
0.042
0.044
0.046
0.047
SRPC 100%
0.08
0.07
Expansion %
0.06
0.05
Prism 1
0.04
Prism 2
0.03
Prism 3
0.02
Prism 4
0.01
0
0
56
112
168
224
280
336
392
448
Days Exposure
Days
0
28
56
84
112
140
168
196
224
252
280
308
336
364
392
420
L (%)P1
0
0
0
0.003
0.008
0.012
0.015
0.022
0.024
0.024
0.032
0.041
0.048
0.051
0.064
0.071
L (%)P2
0
0
0.003
0.007
0.012
0.016
0.02
0.024
0.029
0.031
0.036
0.044
0.053
0.059
0.068
0.075
L (%)P3
0
0
0.002
0.004
0.01
0.014
0.018
0.023
0.027
0.031
0.036
0.044
0.051
0.058
0.067
0.073
L (%)P4
0
0.001
0.006
0.009
0.012
0.014
0.019
0.023
0.026
0.028
0.028
0.037
0.042
0.045
0.054
0.06
Results Contd: Expansion vs time 0.5
CEM II 100%
0.18
0.16
Expansion (%)
0.14
0.12
0.1
0.08
0.06
0.04
0.02
0
0
10
15
20
25
20
25
Time ^ 0.5(Days)
CEM II + 50% GGBS

0.035
0.03
Expansion (%)
0.025
0.02
0.015
0.01
0.005
0
0
10
15
Time ^ 0.5(Days)
CEM II + 70% GBS

0.04
0.035
Expansion (%)
0.03
0.025
0.02
0.015
0.01
0.005
0
0
10
12
14
16
18
20
Time ^ 0.5(Days)
CEM I 100%
0.4
0.35
Expansion (%)
0.3
0.25
0.2
0.15
0.1
0.05
0
0
10
15
Time ^ 0.5(Days)
20
25
CEM I + 70% GGBS

0.045
0.04
Expansion (%)
0.035
0.03
0.025
0.02
0.015
0.01
0.005
0
0
10
15
20
25
20
25
Time ^ 0.5(Days)
SRPC 100%
0.08
0.07
Expansion (%)
0.06
0.05
0.04
0.03
0.02
0.01
0
0
10
15
Time ^ 0.5(Days)
APPENDIX D: Concrete Permeability and Sorption Tests

Air permeability results
MA53
5.9
6.05
5.8
5.7
5.6
y = -0.054x + 6.2021
5.5
5.85
5.3
5.7
5
10
Time (mins)
15
20
MB15
Ln(Pressure)
5.8
5.7
5.6
y = -0.0473x + 6.1426
5.5
5.4
0
10
Time mins)
15
10
Time (mins)
15
20
15
20
15
20
y = -0.013x + 6.200
10
Time (mins)
MC16
6.15
5.9
6.1
Ln(Pressure)
5.8
5.7
5.6
5.5
MB16
6.16
6.14
6.12
6.1
6.08
6.06
6.04
6.02
6
5.98
20
MC15
y = -0.0283x + 6.1883
5.8
5.9
Ln(Pressure)
5.9
5.75
Ln(Pressure)
5.95
5.4
0
MA16
6.1
Ln(Pressure)
Ln(Pressure)
y = -0.0555x + 6.2162
6.05
6
y = -0.018x + 6.221
5.95
5.4
5.3
5.9
0
10
Time (mins)
15
20
10
Time (mins)
MD15
6.15
Ln(Pressure)
Ln(Pressure)
5.8
5.6
5.4
5.2
y = -0.0738x + 6.1296
6.1
6.05
4.8
5.95
0
10
Time (mins)
15
20
10
Ln(Pressure)
6.05
6
5.95
5.9
5.85
5.8
5.75 y = -0.0345x + 6.1994
5.7
5.65
15
y = -0.015x + 6.224
ME15
Ln(Pressure)
MD16
6.2
20
10
15
20
15
20
Time (mins)
SR15
SR16
6.2
6.19
Ln(Pressure)
5.6
Ln(Pressure)
15
y = -0.014x + 6.235
Time (mins)
5.8
10
Time (mins)
ME16
6.18
6.16
6.14
6.12
6.1
6.08
6.06
6.04
6.02
6
20
5.4
5.2
y = -0.082x + 6.1198
6.18
6.17
6.16
6.15
y = -0.006x + 6.223
6.14
4.8
6.13
0
10
Time (mins)
15
20
10
Time (mins)
Water permeability results
MA53
2.00E-07
MA16
7E-08
6E-08
1.00E-07
y = 3.87E-08x + 1.23E-08
5.00E-08
Water (m3)
Water (m3)
1.50E-07
5E-08
4E-08
3E-08
y = 1.78E-08x - 9.05E-09
2E-08
1E-08
0
0.00E+00
2
2.5
3
Time ^0.5
3.5
MB15
2.00E-07
2.5
3
Time ^0.5
3.5
MB16
7E-08
6E-08
1.00E-07
y = 2.35E-08x + 6.28E-08
5.00E-08
Water (m3)
Water (m3)
1.50E-07
5E-08
4E-08
3E-08
y = 1.30E-08x + 1.40E-08
2E-08
1E-08
0.00E+00
0
2
3
Time ^0.5
3.5
MC15
1.40E-07
1.20E-07
1.20E-07
1.00E-07
1.00E-07
8.00E-08
6.00E-08
4.00E-08
y = 3.12E-08x - 2.85E-09
0.00E+00
Time ^0.5
3.5
MC16
4.00E-08
0.00E+00
3
3.5
6.00E-08
2.00E-08
2.5
3
Time ^0.5
8.00E-08
2.00E-08
2
2.5
1.40E-07
Water (m3)
Water (m3)
2.5
y = 1.96E-08x + 3.96E-08
2.5
3
Time ^0.5
3.5
MD15
3.00E-07
1.20E-07
2.50E-07
1.00E-07
2.00E-07
1.50E-07
1.00E-07
y = 7.57E-08x + 1.96E-08
4.00E-08
0.00E+00
0.00E+00
2.5
3
Time ^0.5
3.5
ME15
y = 2.68E-08x + 1.26E-08
2.5
3
Time ^0.5
3.5
ME16
0.0000001
8E-08
1.00E-07
y = 4.07E-08x + 1.49E-08
5.00E-08
Water (m3)
1.50E-07
Water (m3)
6.00E-08
5.00E-08
2.00E-07
6E-08
4E-08
y = 2.15E-08x - 1.58E-09
2E-08
0
0.00E+00
2
2.5
3
Time ^0.5
3.5
2.5
3.5
Time ^0.5
SR15
3.00E-07
SR16
1.00E-07
2.50E-07
8.00E-08
2.00E-07
1.50E-07
y = 6.44E-08x + 2.96E-08
1.00E-07
Water (m3)
Water (m3)
8.00E-08
2.00E-08
MD16
1.40E-07
Water (m3)
Water (m3)
3.50E-07
6.00E-08
4.00E-08
y = 2.25E-08x + 5.29E-09
5.00E-08
2.00E-08
0.00E+00
0.00E+00
2
2.5
3
Time ^0.5
3.5
2.5
3
Time ^0.5
3.5
Water sorptivity
MA53
MA16
1.20E-07
5E-08
1.00E-07
4E-08
8.00E-08
Water (m3)
Water (m3)
6E-08
3E-08
2E-08
6.00E-08
4.00E-08
y = 2.27E-08x + 1.59E-08
y = 1.56E-08x - 6.25E-09
1E-08
2.00E-08
0.00E+00
2
2.5
3.5
2.5
Time ^0.5
Water (m3)
Water (m3)
2.5E-08
2E-08
1.5E-08
1E-08
y = 5.07E-09x + 6.55E-09
5E-09
0
2
2.5
3.5
y = 4.04E-09x + 1.76E-08
2.5
3.5
Time ^0.5
MC15
MC16
3E-08
1.00E-07
2.5E-08
8.00E-08
2E-08
Water (m3)
Water (m3)
MB16
4E-08
3.5E-08
3E-08
2.5E-08
2E-08
1.5E-08
1E-08
5E-09
0
Time ^0.5
1.20E-07
3.5
Time ^0.5
MB15
3E-08
6.00E-08
4.00E-08
1.5E-08
1E-08
y = 2.59E-08x - 4.23E-09
2.00E-08
5E-09
0.00E+00
0
2
2.5
3
Time ^0.5
3.5
y = 1.59E-08x - 3.35E-08
2.5
3
Time ^0.5
3.5
MD15
2.00E-07
4E-08
Water (m3)
1.50E-07
Water (m3)
MD16
5E-08
1.00E-07
y = 3.97E-08x + 2.36E-08
5.00E-08
3E-08
2E-08
y = 1.45E-08x - 1.21E-08
1E-08
0.00E+00
0
2
2.5
3.5
2.5
Time ^0.5
3.5
Time ^0.5
ME15
8E-08
ME16
1.2E-07
7E-08
1.0E-07
Water (m3)
Water (m3)
6E-08
5E-08
4E-08
3E-08
2E-08
8.0E-08
6.0E-08
4.0E-08
y = 2.66E-08x + 5.75E-09
y = 2.44E-08x - 2.35E-08
1E-08
2.0E-08
0.0E+00
2
2.5
3.5
2.5
Time ^0.5
6E-08
SR15
2.50E-07
3.5
SR16
5E-08
Water (m3)
2.00E-07
Water (m3)
3
Time ^0.5
1.50E-07
1.00E-07
y = 5.35E-08x + 2.76E-08
5.00E-08
4E-08
3E-08
2E-08
1E-08
0
0.00E+00
2
2.5
3
Time ^0.5
3.5
2.5
3
Time ^0.5
3.5
APPENDIX E: Sulfuric Acid Testing: Mass Loss Data (brushed)

MASS (g)
CUBE No.
5
15
16
6
7
8
9
10
11
12
13
14
Prism No.
1
2
3
4
MASS
(g/m2)
CUBE No.
5
15
16
6
7
8
9
10
11
12
13
14
PRISM No.
1
2
3
4
WEEK
0
2447
2434
2443
2436
2449
2448
2453
2456
2453
2487
2462
2473
1
2449
2437
2445
2438
2451
2451
2461
2464
2462
2511
2487
2500
2
2448
2436
2444
2438
2451
2451
2468
2473
2472
2517
2493
2502
3
2449
2435
2443
2439
2451
2451
2446
2449
2448
2498
2475
2486
4
2453
2435
2445
2439
2455
2452
2442
2446
2444
2497
2473
2485
12
2436
2446
3549
3535
3572
3596
3550
3527
3582
3611
3548
3526
3593
3623
3550
3528
3569
3588
3544
3528
3570
3582
16
MIX
20
MA
24
2446
2447
2446
2446
2453
2453
2454
2454
2454
2454
2357
2344
2238
2147
2071
1999
2406
2415
2318
2242
2170
2104
3550
3527
3395
3422
3551
3528
3227
3256
3551
3528
3101
3128
3550
3529
2996
3018
3552
3529
2891
2919
MIX
MA
WEEK
0
0
0
0
0
0
0
0
0
0
0
0
0
1
33
50
33
33
33
50
133
133
150
436
455
491
2
17
33
17
33
33
50
250
283
317
545
564
527
3
33
17
0
50
33
50
-117
-117
-83
200
236
236
4
100
17
33
50
100
67
-183
-167
-150
182
200
218
12
16
20
24
50
0
67
83
50
67
50
50
100
100
100
100
0
0
0
0
12
-93
116
174
-12
-104
243
313
12
-81
-35
-93
-58
-81
-23
-162
12
-93
-2052
-2017
-1650
-1817 -3583 -5100 -6367 -7567
-1018
-1055 -2818 -4200 -5509 -6709
23
-81
-4000
-3942
23
-81
-5461
-5426
12
-70
-6678
-6701
35
-70
-7896
-7849
MASS (g)
CUBE No.
3
4
5
6
7
8
9
10
11
12
13
14
PRISM No.
1
2
3
4
MASS
(g/m2)
CUBE No.
3
4
5
6
7
8
9
10
11
12
13
14
PRISM No.
1
2
3
4
WEEK
0
2423
2434
2421
2424
2423
2436
2445
2429
2442
2485
2485
2456
1
2426
2436
2422
2426
2426
2437
2441
2425
2440
2484
2485
2452
2
2426
2436
2422
2427
2424
2438
2438
2426
2434
2488
2487
2455
3
2426
2437
2423
2426
2425
2436
2422
2405
2417
2467
2472
2435
4
2424
2436
2422
2425
2425
2437
2411
2394
2406
2458
2463
2427
12
2422
2425
2425
2437
3485
3468
3494
3498
3486
3470
3483
3496
3487
3470
3488
3504
3484
3468
3466
3480
3485
3470
3448
3463
16
MIX
20
MB
24
2423
2423
2423
2424
2438
2438
2438
2438
2273
2281
2175
2099
2016
1956
2361
2325
2238
2161
2082
2019
3485
3470
3281
3303
3486
3470
3138
3156
3487
3470
3022
3044
3486
3471
2903
2931
3487
3473
2814
2845
MIX
MB
WEEK
0
0
0
0
0
0
0
0
0
0
0
0
0
1
50
33
17
33
50
17
-67
-67
-33
-18
0
-73
2
50
33
17
50
17
33
-117
-50
-133
55
36
-18
3
50
50
33
33
33
0
-383
-400
-417
-327
-236
-382
4
17
33
17
17
33
17
-567
-583
-600
-491
-400
-527
12
16
20
24
17
17
33
17
33
33
33
50
33
33
33
33
0
0
0
0
12
23
-128
-23
23
23
-70
70
-12
0
-325
-209
0
23
-533
-406
0
23
-2470
-2261
-2600
-2683 -4450 -5717 -7100 -8100
-2255
-2382 -3964 -5364 -6800 -7945
12
23
-4128
-3965
23
23
-5472
-5264
12
35
-6852
-6574
23
58
-7884
-7571
MASS (g)
CUBE No.
3
4
5
6
7
8
9
10
11
12
13
14
PRISM No.
1
2
3
4
MASS
(g/m2)
CUBE No.
3
4
5
6
7
8
9
10
11
12
13
14
PRISM No.
1
2
3
4
WEEK
0
2437
2434
2439
2421
2439
2438
2407
2435
2447
2478
2494
2472
1
2438
2437
2441
2424
2440
2440
2404
2433
2443
2478
2498
2475
2
2439
2436
2441
2425
2441
2440
2410
2439
2451
2485
2504
2481
3
2438
2436
2441
2423
2441
2439
2394
2427
2438
2471
2491
2470
4
2437
2435
2440
2423
2440
2439
2387
2420
2424
2461
2482
2457
3449
3472
3515
3475
3451
3477
3512
3476
3452
3476
3520
3486
3452
3475
3507
3471
3450
3476
3494
3452
3450
3475
3370
3334
12
MIX MC
20
24
16
2441 2442 2442 2440 2442

2424
2441
2439 2440 2440 2438 2441
2311
2311 2205 2122 2051 1986
2379
2353 2272 2198 2135 2078
3452
3476
3228
3193
3451
3475
3107
3064
3450
3475
2998
2957
3453
3478
2912
2868
MIX
MC
WEEK
0
0
0
0
0
0
0
0
0
0
0
0
0
1
17
50
33
50
17
33
-50
-33
-67
0
73
55
2
33
33
33
67
33
33
50
67
67
127
182
164
3
17
33
33
33
33
17
-217
-133
-150
-127
-55
-36
4
0
17
17
33
17
17
-333
-250
-383
-309
-218
-273
12
16
20
24
33
50
33
17
50
50
17
50
33
33
50
0
0
0
0
23
58
-35
12
35
46
58
128
35
35
-93
-46
12
46
-243
-267
12
35
-1681
-1635
-2067
-2267 -4033 -5417 -6600 -7683
-2091
-2164 -3636 -4982 -6127 -7164
35
46
-3328
-3270
23
35
-4730
-4765
12
35
-5994
-6006
46
70
-6991
-7038
MASS (g)
CUBE No.
3
4
5
6
7
8
9
10
11
12
13
14
PRISM No.
1
2
3
4
MASS
(g/m2)
CUBE No.
3
4
5
6
7
8
9
10
11
12
13
14
Prism No.
1
2
3
4
WEEK
0
2519
2516
2516
2527
2515
2500
2450
2446
2446
2502
2496
2481
1
2522
2518
2519
2529
2517
2504
2435
2433
2432
2496
2496
2480
2
2522
2518
2518
2529
2517
2502
2436
2434
2432
2497
2496
2481
3
2521
2518
2518
2529
2516
2503
2419
2419
2414
2482
2481
2468
4
2520
2517
2518
2528
2517
2502
2409
2411
2404
2475
2474
2457
3527
3499
3512
3503
3528
3504
3497
3484
3530
3505
3497
3489
3530
3503
3477
3461
3528
3502
3464
3444
3529
3503
3325
3297
WEEK
0
0
0
0
0
0
0
0
0
0
0
0
0
1
50
33
50
33
33
67
-250
-217
-233
-109
0
-18
2
50
33
33
33
33
33
-233
-200
-233
-91
0
0
3
33
33
33
33
17
50
-517
-450
-533
-364
-273
-236
4
17
17
33
17
33
33
-683
-583
-700
-491
-400
-436
0
0
0
0
12
58
-174
-220
35
70
-174
-162
35
46
-406
-487
12
35
-557
-684
12
16
MIX MD
20
24
2518 2519 2519 2519 2518

2529
2517
2503 2504 2503 2503 2502
2298
2297 2191 2104 2020 1957
2377
2364 2270 2199 2124 2063
3531
3503
3174
3136
3530
3504
3061
3024
3532
3504
2950
2916
3531
3504
2867
2838
MIX
MD
12
16
20
24
33
33
33
50
50
50
50
33
67
50
50
33
-2467
-2483 -4250 -5700 -7100 -8150
-2164
-2127 -3836 -5127 -6491 -7600
23
46
-2168
-2388
46
46
-3919
-4255
35
58
-5229
-5554
58
58
-6516
-6806
46
58
-7478
-7710
MASS (g)
CUBE No.
3
4
5
6
7
8
9
10
11
12
13
14
PRISM No.
1
2
3
4
MASS
(g/m2)
CUBE No.
3
4
5
6
7
8
9
10
11
12
13
14
PRISM No.
1
2
3
4
WEEK
0
2447
2437
2423
2427
2411
2446
2432
2420
2433
2471
2486
2470
1
2450
2437
2424
2427
2412
2449
2432
2422
2435
2483
2493
2480
2
2448
2440
2424
2427
2413
2448
2437
2425
2440
2486
2498
2484
3
2448
2438
2425
2428
2413
2448
2416
2407
2418
2460
2481
2464
4
2448
2438
2425
2427
2413
2448
2408
2396
2409
2458
2472
2455
3532
3471
3494
3469
3536
3476
3468
3489
3537
3476
3492
3478
3536
3475
3473
3451
3536
3473
3460
3440
3536
3474
3331
3329
12
16
MIX ME
20
24
2425 2426 2425 2425 2426

2428
2413
2448 2449 2448 2449 2449
2303
2313 2210 2127 2042 1982
2386
2372 2284 2215 2144 2080
3536
3475
3198
3199
3535
3475
3084
3076
3535
3476
2974
2952
3535
3476
2896
2870
MIX
ME
WEEK
0
0
0
0
0
0
0
0
0
0
0
0
0
1
50
0
17
0
17
50
0
33
33
218
127
182
2
17
50
17
0
33
33
83
83
117
273
218
255
3
17
17
33
17
33
33
-267
-217
-250
-200
-91
-109
4
17
17
33
0
33
33
-400
-400
-400
-236
-255
-273
12
16
20
24
33
17
33
33
50
33
33
50
50
33
50
50
0
0
0
0
46
58
-301
232
58
58
-23
104
46
46
-243
-209
46
23
-394
-336
46
35
-1890
-1623
-1950
-2000 -3717 -5100 -6517 -7517
-1818
-1782 -3382 -4636 -5927 -7091
46
46
-3432
-3130
35
46
-4754
-4557
35
58
-6029
-5994
35
58
-6933
-6945
MASS (g)
CUBE No.
3
4
5
6
7
8
9
10
11
12
13
14
PRISM No.
1
2
3
4
MASS
(g/m2)
CUBE No.
3
4
5
6
7
8
9
10
11
12
13
14
PRISM No.
1
2
3
4
WEEK
0
2481
2459
2470
2478
2482
2458
2461
2478
2464
2520
2509
2522
1
2482
2461
2471
2480
2483
2461
2451
2472
2452
2526
2514
2530
2
2482
2462
2472
2479
2483
2460
2448
2469
2450
2524
2512
2529
3
2482
2460
2471
2480
2483
2460
2431
2447
2434
2508
2498
2512
4
2482
2460
2471
2480
2483
2460
2423
2437
2425
2500
2490
2507
3543
3550
3542
3555
3546
3551
3541
3556
3546
3549
3537
3552
3546
3550
3512
3524
3545
3550
3504
3514
3545
3550
3395
3395
12
16
MIX SR
20
24
2461
2472 2472 2472 2472 2471
2484
2461 2462 2461 2462 2460
2337
2326 2190 2105 2028 1962
2415
2421 2309 2232 2159 2092
3546
3552
3211
3205
3546
3553
3075
3077
3547
3553
2965
2968
3548
3553
2875
2881
MIX
SR
WEEK
0
0
0
0
0
0
0
0
0
0
0
0
0
1
17
33
17
33
17
50
-167
-100
-200
109
91
145
2
17
50
33
17
17
33
-217
-150
-233
73
55
127
3
17
17
17
33
17
33
-500
-517
-500
-218
-200
-182
4
17
17
17
33
17
33
-633
-683
-650
-364
-345
-273
12
16
20
24
33
33
33
33
33
17
33
50
67
50
67
33
0
0
0
0
35
12
-12
12
35
-12
-58
-35
35
0
-348
-359
23
0
-441
-475
23
0
-1704
-1855
-2350
-2300 -4567 -5983 -7267 -8367
-1709
-1836 -3873 -5273 -6600 -7818
35
23
-3838
-4058
35
35
-5414
-5542
46
35
-6690
-6806
58
35
-7733
-7814
Mass Loss (g/m2)
Week
MA
MB
MC
MD
ME
SR
261
51
153
66
15
380
25
105
137
139
55
29
335
107
408
198
353
11
513
285
567
337
483
1601
2442
1984
2300
1844
1959
12
3586
4127
3567
4065
3415
4084
16
5047
5454
4974
5402
4762
5553
20
6314
6832
6182
6728
6117
6841
24
7505
7875
7219
7735
7121
7933
APPENDIX F: Sulfuric Acid Testing: Mass Loss Data (unbrushed)

MASS (g)
CUBE No.
17
18
MASS
(g/m2)
CUBE No.
17
18
WEEK
0
1
2
3
4
8
12
16
2468
2473 2480 2482 2478 2406 2304 2258
2472
2477 2486 2488 2487 2426 2318 2275
MASS (g)
CUBE No.
17
18
MIX
20
2219
2226
MIX
MA
WEEK
0
1 2
3
4
8
12
16
20
24
0
91 218 255 182 -1127 -2982 -3818 -4527 -5091
0
91 255 291 273 -836 -2800 -3582 -4473 -4927
WEEK
0
1
2
3
4
8
12
16
2469
2484 2498 2516 2512 2390 2294 2258
2494
2511 2526 2542 2548 2409 2310 2272
MIX
20
2220
2239
MASS
(g/m2)
CUBE No.
17
18
MIX
WEEK
0
1
2
3
4
8
12
16
20
0
273 527 855 782 -1436 -3182 -3836 -4527
0
309 582 873 982 -1545 -3345 -4036 -4636
MASS (g)
CUBE No.
17
18
WEEK
0
1
2
3
4
8
12
16
2459
2482 2496 2516 2529 2394 2299 2255
2484
2477 2517 2534 2549 2426 2329 2291
MASS
(g/m2)
CUBE No.
17
18
MA
24
2188
2201
MB
24
2213
2230
MB
24
-4655
-4800
MIX
20
2224
2262
MC
24
2231
2257
MIX
MC
WEEK
0
1
2
3
4
8
12
16
20
24
0
418 673 1036 1273 -1182 -2909 -3709 -4273 -4145
0
-127 600 909 1182 -1055 -2818 -3509 -4036 -4127
MASS (g)
CUBE No.
17
18
WEEK
0
1
2
3
4
8
12
16
2553
2563 2575 2580 2581 2471 2378 2331
2544
2557 2569 2580 2578 2453 2366 2325
MIX
20
2287
2286
MD
24
2266
2267
MASS
(g/m2)
CUBE No.
17
18
WEEK
0
1
2
3
4
8
12
16
20
24
0
182 400 491 509 -1491 -3182 -4036 -4836 -5218
0
236 455 655 618 -1655 -3236 -3982 -4691 -5036
MASS (g)
CUBE No.
17
18
WEEK
0
1
2
3
4
8
12
16
2478
2498 2512 2525 2534 2424 2326 2281
2483
2503 2513 2531 2541 2424 2338 2288
MASS
(g/m2)
CUBE No.
17
18
MIX
WEEK
0
1
2
3
4
8
12
16
20
0
364 618 855 1018 -982 -2764 -3582 -4000
0
364 545 873 1055 -1073 -2636 -3545 -4055
ME
MASS (g)
CUBE No.
17
18
WEEK
0
1
2
3
4
8
12
16
2510
2526 2540 2549 2540 2435 2337 2291
2529
2549 2556 2557 2552 2459 2351 2303
SR
24
2220
2229
MIX
MASS
(g/m2)
WEEK
CUBE No. 0
1
2
3
4
8
12
16
0
291 545 709 545 -1364 -3145 -3982
0
364 491 509 418 -1273 -3236 -4109
MIX
20
2258
2260
MIX
20
2245
2257
MIX
MD
ME
24
2262
2260
24
-3927
-4055
SR
20
24
-4818 -5273
-4945 -5455
Mass Loss (g/m2)
Week
MA
MB
MC
MD
ME
SR
61
194
97
140
243
219
158
370
425
286
389
346
183
577
649
377
577
407
153
589
820
383
692
323
982
1491
1118
1573
1027
1318
12
2891
3264
2864
3209
2700
3191
16
3700
3936
3609
4009
3564
4045
20
4500
4582
4155
4764
4027
4882
24
5009
4727
4136
5127
3991
5364
APPENDIX G: Sulfuric Acid Testing: Cube Strength Data
Days
Water
Acid
% Loss
0
28
56
168
57
57
58
60
57
50
35
21
0%
12%
40%
65%
Cube strength (MPa)
Compressive Strength: Mix MA
80
70
60
50
40
30
20
10
0
Cubes in water
Cubes in acid
Days
Water
Acid
% Loss
0
28
56
168
61
65
65
70
61
53
35
19
0%
18%
46%
74%
Cube strength (MPa)
Compressive Strength: Mix MB
28
56
84
Days
112
140
168
80
70
60
50
40
30
20
10
Cubes in water
Cubes in acid
0
0
Days
0
28
56
168
Water
58
58
63
65
Acid
58
51
37
22
% Loss
0%
12%
42%
66%
Cube strength (MPa)
Compressive Strength: Mix MC
28
56
84
Days
112
140
168
80
70
60
50
40
30
20
10
0
Cubes in water
Cubes in acid
28
56
84
Days
112
140
168
Days
0
28
56
168
Water
65
71
75
77
Acid
65
56
43
19
% Loss
0%
21%
42%
76%
Cube strength (MPa)
Compressive Strength: Mix MD
MD - 100% CEM I
80
70
60
50
40
30
20
10
0
Cubes in water
Cubes in acid
Days
0
28
56
168
Water
54
57
59
69
Acid
54
49
34
18
% Loss
0%
14%
42%
74%
Cube strength (MPa
Compressive Strength: Mix ME
28
56
84
Days
112
140
168
140
168
140
168
80
70
60
50
40
30
20
10
0
Cubes in water
Cubes in acid
28
56
84
112
Days
Days
0
28
56
168
Water
60
58
68
75
Acid
60
59
41
21
% Loss
0%
0%
40%
72%
Cube Strength (Mpa)
Compressive Strength: Mix SR
SR - 100% SRPC
80
70
60
50
40
30
20
10
0
Cubes in water
Cubes in acid
28
56
84
Days
112
APPENDIX H: Sulfuric Acid Testing: Expansion Data

MB1 WATER
Wk 0
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
MB3 ACID
Ref Bar
(mm)
6.62
6.717
5.79
5.852
6.454
6.46
6.147
6.151
6.052
6.059
6.242
6.249
6.599
6.608
Ref Bar
(mm)
Reading
(mm)
3.332
3.42
2.501
2.557
3.158
3.158
2.83
2.862
2.748
2.752
2.948
2.949
3.298
3.301
Reading
(mm)
L
(%)
MB2 WATER
Wk 0
0.003
0.001
0.000
-0.002
-0.008
0.003
-0.003
-0.004
0.001
-0.001
-0.002
-0.004
L
(%)
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
MB4 ACID
Wk 0
Wk 0
Wk 4
Wk 4
Wk 8
Wk 8
NO READINGS
Wk 12
Wk 12
Wk 16
Wk 16
Wk 20
Wk 20
Wk 24
Wk 24
Ref Bar
(mm)
6.634
6.732
5.814
5.869
6.46
6.46
6.146
6.153
6.055
6.059
6.246
6.251
6.606
6.61
Ref Bar
(mm)
6.689
6.779
5.85
5.88
6.46
6.461
6.151
6.081
6.058
6.06
6.249
6.252
6.608
Reading
(mm)
3.517
3.601
2.661
2.712
3.299
3.304
3.001
2.976
2.888
2.885
3.082
3.083
3.435
3.434
Reading
(mm)
3.48
3.558
2.687
2.668
3.226
2.862
2.823
2.807
2.798
2.989
2.992
3.344
L
(%)
-0.009
-0.010
-0.012
-0.010
-0.006
-0.018
-0.014
-0.017
-0.013
-0.015
-0.016
-0.018
L
(%)
0.023
0.004
-0.005
-0.008
-0.027
-0.015
-0.012
-0.016
-0.016
-0.016
-0.017
MB1 WATER
Wk 0
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
MB3 ACID
Wk 0
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
Ref Bar
(mm)
5.981
5.989
6.618
6.851
6.189
6.192
6.436
6.424
6.229
6.249
6.596
6.621
6.433
6.439
Ref Bar
(mm)
5.975
5.997
6.802
6.882
6.191
6.192
6.258
6.47
6.243
6.252
6.61
6.621
6.438
6.438
Reading
(mm)
2.621
2.625
3.345
3.476
2.807
2.823
3.138
3.047
2.887
2.861
3.213
3.23
3.046
3.047
Reading
(mm)
2.884
2.874
3.685
3.725
3.031
3.039
3.22
3.328
3.056
3.082
3.427
3.424
3.311
3.222
L
(%)
MB2 WATER
Wk 0
0.036
-0.004
-0.007
-0.002
0.026
-0.005
0.009
-0.010
-0.008
-0.011
-0.009
-0.011
L
(%)
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
MB4 ACID
Wk 0
0.002
-0.014
-0.015
-0.012
0.034
-0.008
-0.026
-0.019
-0.024
-0.030
-0.002
-0.037
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
6.608
Ref Bar
(mm)
5.956
5.994
6.664
6.869
6.19
6.192
6.234
6.448
6.232
6.251
6.605
6.62
6.437
6.439
Ref Bar
(mm)
5.985
6
6.848
6.883
6.192
6.192
6.396
6.484
6.245
6.254
6.624
6.618
6.438
6.431
3.347
Reading
(mm)
2.75
2.761
3.422
3.631
2.942
2.937
3.014
3.209
2.99
3.005
3.352
3.357
3.176
3.178
Reading
(mm)
2.851
2.822
3.625
3.665
2.981
2.976
3.188
3.246
3.013
3.019
3.354
3.372
3.177
3.171
-0.016
L
(%)
-0.004
-0.002
-0.006
-0.009
0.005
-0.002
-0.004
-0.005
-0.008
-0.012
-0.011
-0.011
L
(%)
-0.018
-0.016
-0.013
-0.015
-0.012
-0.024
-0.022
-0.023
-0.037
-0.027
-0.033
-0.033
MC1 WATER
Wk 0
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
MC3 ACID
Wk 0
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
Ref Bar
(mm)
6.135
6.132
6.034
6.038
6.214
6.244
6.05
6.058
6.25
6.248
6.612
6.62
6.434
6.434
Ref Bar
(mm)
6.133
6.133
6.035
6.039
6.233
6.247
6.058
6.056
6.251
6.253
6.614
6.619
6.437
6.438
Reading
(mm)
3.182
3.172
3.07
3.064
3.224
3.277
3.075
3.075
3.276
3.273
3.635
3.635
3.451
3.451
Reading
(mm)
2.949
2.951
2.833
2.83
3.07
3.037
2.829
2.831
3.015
3.016
3.385
3.379
3.196
3.194
L
(%)
MC2 WATER
Wk 0
-0.002
-0.006
-0.012
-0.003
-0.006
-0.009
-0.006
-0.006
-0.007
-0.010
-0.009
-0.009
L
(%)
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
MC4 ACID
Wk 0
-0.007
-0.010
0.008
-0.010
-0.018
-0.016
-0.021
-0.021
-0.018
-0.022
-0.023
-0.024
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
Ref Bar
(mm)
6.134
6.133
6.035
6.039
6.212
6.247
6.057
6.059
6.25
6.252
6.612
6.619
6.435
6.436
Ref Bar
(mm)
6.132
6.132
6.033
6.039
6.241
6.247
6.054
6.059
6.244
6.251
6.616
6.62
6.433
6.437
Reading
(mm)
3.085
3.076
2.885
2.893
3.157
3.142
2.895
2.833
3.027
3.045
3.386
3.381
3.203
3.202
Reading
(mm)
3.017
2.881
2.721
2.724
2.959
2.93
2.74
2.73
2.917
2.918
3.386
3.29
3.088
3.091
L
(%)
-0.037
-0.036
0.001
-0.019
-0.042
-0.068
-0.066
-0.060
-0.068
-0.072
-0.070
-0.071
L
(%)
-0.024
-0.026
-0.012
-0.026
-0.025
-0.031
-0.030
-0.033
0.008
-0.032
-0.038
-0.038
MD1 WATER
Wk 0
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
MD3 ACID
Wk 0
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
Ref Bar
(mm)
6.147
6.15
6.463
6.468
6.242
6.249
6.054
6.056
6.249
6.253
6.61
6.612
6.444
6.446
Ref Bar
(mm)
6.149
6.15
6.466
6.464
6.248
6.25
6.056
6.059
6.252
6.255
6.611
6.612
6.443
6.446
Reading
(mm)
3.134
3.1
3.374
3.396
3.141
3.145
2.951
2.953
3.145
3.148
3.502
3.495
3.32
3.323
Reading
(mm)
3.042
3.013
3.235
3.226
2.995
3.01
2.8
2.803
2.986
2.982
3.338
3.331
3.151
3.153
L
(%)
MD2 WATER
Wk 0
-0.016
-0.009
-0.020
-0.022
-0.021
-0.021
-0.022
-0.022
-0.023
-0.027
-0.030
-0.029
L
(%)
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
MD4 ACID
Wk 0
-0.038
-0.040
-0.046
-0.041
-0.048
-0.048
-0.052
-0.054
-0.054
-0.058
-0.062
-0.062
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
Ref Bar
(mm)
6.152
6.15
6.466
6.466
6.246
6.25
6.055
6.057
6.25
6.255
6.611
6.612
6.443
6.446
Ref Bar
(mm)
6.151
6.15
6.464
6.464
6.246
6.25
6.054
6.056
6.253
6.257
6.611
6.611
6.444
6.447
Reading
(mm)
2.98
2.966
3.298
3.274
3.219
3.108
2.98
2.884
3.114
3.07
3.432
3.427
2.253
3.254
Reading
(mm)
3.132
3.162
3.402
3.399
3.172
3.163
2.984
2.969
3.169
3.162
3.514
3.517
3.334
3.334
L
(%)
0.006
-0.003
0.063
0.017
0.044
0.004
0.019
0.000
0.002
0.000
-0.402
-0.003
L
(%)
-0.017
-0.018
-0.022
-0.027
-0.020
-0.027
-0.026
-0.030
-0.031
-0.030
-0.036
-0.038
ME1 WATER
Wk 0
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
ME3 ACID
Wk 0
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
Ref Bar
(mm)
5.962
5.819
6.464
6.444
6.148
6.153
6.049
6.053
6.253
6.254
6.614
6.616
6.44
6.443
Ref Bar
(mm)
5.964
5.716
6.467
6.46
6.153
6.153
6.052
6.054
6.253
6.254
6.615
6.616
6.443
6.443
Reading
(mm)
2.717
2.559
3.215
3.187
2.891
2.883
2.794
2.794
2.989
2.985
3.348
3.347
3.174
3.174
Reading
(mm)
2.662
2.574
3.209
3.259
2.988
2.981
2.882
2.87
3.075
3.062
3.405
3.402
3.222
3.213
L
(%)
ME2 WATER
Wk 0
0.004
0.001
0.001
-0.004
0.002
0.000
-0.002
-0.004
-0.002
-0.004
-0.002
-0.004
L
(%)
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
ME4 ACID
Wk 0
0.018
0.040
0.055
0.052
0.053
0.047
0.050
0.044
0.037
0.035
0.032
0.029
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
Ref Bar
(mm)
5.964
5.825
6.466
6.434
6.152
6.153
6.051
6.055
6.253
6.254
6.615
6.616
6.441
6.442
Ref Bar
(mm)
5.797
5.732
6.466
6.466
6.151
6.153
6.054
6.055
6.25
6.257
6.615
6.616
6.442
6.443
Reading
(mm)
2.876
2.732
3.372
3.337
3.047
3.043
2.995
2.959
3.148
3.147
3.508
3.506
3.332
3.33
Reading
(mm)
2.582
2.51
3.254
3.257
2.893
2.907
2.787
2.789
2.982
2.981
3.34
3.339
3.158
3.156
L
(%)
0.000
-0.002
-0.005
-0.007
0.015
-0.001
-0.005
-0.006
-0.006
-0.007
-0.006
-0.008
L
(%)
0.004
0.005
-0.014
-0.010
-0.018
-0.018
-0.018
-0.022
-0.021
-0.022
-0.025
-0.026
SR1 WATER
Wk 0
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
SR3 ACID
Wk 0
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
Ref Bar
(mm)
5.683
5.955
6.458
6.464
6.146
6.15
6.054
6.054
6.255
6.229
6.609
6.61
6.442
6.445
Ref Bar
(mm)
5.937
5.956
6.463
6.465
6.15
6.149
6.058
6.056
6.255
6.239
6.611
6.597
6.444
6.445
Reading
(mm)
2.672
2.889
3.224
3.185
2.869
2.853
2.748
2.743
2.942
2.905
3.297
3.297
3.123
3.119
Reading
(mm)
2.681
2.689
3.129
3.119
2.806
2.804
2.696
2.69
2.893
2.87
3.226
3.201
3.053
3.047
L
(%)
SR2 WATER
Wk 0
-0.067
-0.085
-0.084
-0.092
-0.096
-0.098
-0.099
-0.103
-0.098
-0.099
-0.101
-0.104
L
(%)
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
SR4 ACID
Wk 0
-0.027
-0.032
-0.031
-0.031
-0.038
-0.040
-0.038
-0.041
-0.047
-0.052
-0.050
-0.052
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
Ref Bar
(mm)
5.927
5.955
6.461
6.46
6.15
6.152
6.055
6.058
6.255
6.236
6.61
6.608
6.444
6.445
Ref Bar
(mm)
5.95
5.957
6.462
6.461
6.151
6.154
6.059
6.058
6.255
6.245
6.61
6.6
6.444
6.446
Reading
(mm)
2.592
2.631
3.131
3.083
2.817
2.758
2.711
2.678
2.875
2.841
3.222
3.213
3.045
3.044
Reading
(mm)
2.715
2.72
3.162
3.156
2.827
2.825
2.734
2.718
2.88
2.923
3.246
3.228
3.067
3.061
L
(%)
0.002
-0.017
0.001
-0.024
-0.004
-0.018
-0.018
-0.024
-0.021
-0.024
-0.026
-0.026
L
(%)
-0.025
-0.027
-0.035
-0.037
-0.035
-0.041
-0.055
-0.034
-0.051
-0.054
-0.056
-0.059
Cement & Concrete Composites 32 (2010) 479485
Contents lists available at ScienceDirect
Cement & Concrete Composites

journal homepage: www.elsevier.com/locate/cemconcomp
Biochemical attack on concrete in wastewater applications: A state of the art review

M. OConnell, C. McNally *, M.G. Richardson
School of Architecture, Landscape and Civil Engineering, University College Dublin, Newstead, Beleld, Dublin 4, Ireland
a r t i c l e
i n f o
Article history:
Received 14 July 2009
Received in revised form 20 April 2010
Accepted 1 May 2010
Available online 7 May 2010
Keywords:
Sulfate attack
Sulfuric acid
Thiobacillus
Secondary cementitious materials
Performance specications
a b s t r a c t
The costs associated with the provision and maintenance of drinking water and wastewater infrastructure represents a signicant nancial demand worldwide. Maintenance costs are disproportionately high,
indicating a lack of adequate durability. There remains a lack of consensus on degradation mechanisms,
the performance of various cement types, the role of bacteria in the corrosion process associated with
wastewater applications and testing methodologies. This paper presents a review of the literature, outlining the various research approaches undertaken in an effort to address this problem. The ndings of
these varying approaches are compared, and the different strategies employed are compiled and discussed. It is proposed that a key step in advancing the understanding of the associated deterioration
mechanism is a combined approach that considers the interaction between biological and chemical processes. If this can be achieved then steps can be taken to establishing a performance-based approach for
specifying concrete in these harsh service conditions.
2010 Elsevier Ltd. All rights reserved.
1. Introduction
The provision of high quality water and wastewater infrastructure requires signicant international expenditure on concrete
with consequent expectations of lengthy service lives. For example
in the US alone, it is estimated that annual investments of up to
$20 billion and $21 billion is required to provide adequate
infrastructure for drinking water and wastewater respectively
[1]. It is also estimated that the annual operation and maintenance
costs associated with drinking water and wastewater infrastructure to be in excess of $31 billion and $25 billion respectively.
Against this backdrop, it is surprising to note that the corrosion
of water and wastewater infrastructure has been a topic of debate
for decades, with little consensus on the methods for designing and
specifying this infrastructure to optimally meet the harsh environmental demands it will meet in service [27]. The majority of studies to date have focused on the deterioration of concrete in sewer
systems and pipelines [5,8,9]. However little detailed research has
been conducted into the effect of corrosion on the vital treatment
facilities that are processing our wastewater. Concrete pipes in
sewer systems tend to be an off-the-shelf product with little input by the specier into specication of mix design. As a result the
performance of the product is largely dependent on the manufacturers mix design which is inuenced by local factors. In treatment
plants the concrete may be specied by the engineer, but a lack of
in-depth research into the deterioration of these structures has
* Corresponding author. Tel.: +353 1 716 3202; fax: +353 1 716 3297.
E-mail address: ciaran.mcnally@ucd.ie (C. McNally).
0958-9465/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.cemconcomp.2010.05.001
meant little change in professional practice concerning concrete

mix design.
Existing evidence has shown that corrosion is present in many
concrete structures associated with water and wastewater treatment. The alarming fact is that some of these facilities are deteriorating signicantly after less than a decade in service (Fig. 1). In
this context it is clear that current design practices based on prescriptive approaches to concrete specication may not be appropriate to deal with the aggressive nature of wastewater, and in
some cases, the treatment processes involved in drinking water
purication [10]. Existing research ndings are not yet inuencing
current construction practice. The lack of widely quoted durability
design formulae illustrates that the deterioration mechanisms
associated with this critical infrastructural application are not yet
widely accepted or understood. This paper will assist in bridging
this gap by considering the role of key parameters such as environmental conditions, the nature of the attack and the physical results
of the attack on the concrete. This will promote increased understanding of the deterioration mechanism and facilitate the introduction of a performance-based design approach.
2. Characterising the wastewater environment
The deterioration of sewer systems has long been a topic under
considerable scrutiny and in the mid 1940s a comprehensive scientic evaluation was undertaken in an attempt to understand the
corrosion process [11]. Current research has continued to focus
on the deterioration of concrete sewer pipes and case studies have
taken place throughout the world, including comprehensive
480
M. OConnell et al. / Cement & Concrete Composites 32 (2010) 479485
acid reacts with a cement matrix, the rst step involves a reaction
between the acid and the calcium hydroxide (Ca(OH)2) forming
calcium sulfate according to the following equation:
CaOH2 H2 SO4 ! CaSO4 2H2 O
This is subsequently hydrated to form gypsum (CaSO42H2O),

the appearance of which on the surface of concrete pipes takes
the form of a white, mushy substance which has no cohesive properties and has, the consistency of cottage cheese [23]. In the
continuing attack, the gypsum would react with the calcium aluminate hydrate (C3A) to form ettringite, an expansive product:
3CaSO4 2H2 O 3CaOAl2 O3 26H2 O

! CaO3 Al2 O3 CaSO4 3 32H2 O
Fig. 1. Evidence of corrosion in grit removal tanks with gypsum and exposed
aggregate visible above the water line in a wastewater treatment plant constructed
in 2003.
reviews on current infrastructure [8]. In the latter, the condition of

the sewer system in four cities in the Lebanon was evaluated
whereby certain contributory factors in corrosion were outlined:
Biological Oxygen Demand (BOD) levels, high sulfate and dissolved
sulde concentration, high temperatures, high H2S gas concentration, high turbulence and long detention times, low dissolved oxygen levels, low water velocity and low wastewater pH. These and
other criteria have been outlined in several publications, all of
which detail the conditions leading to corrosion in sewer environments [4,5,1214].
The contributory factors outlined above are not only limited to
sewer piping they are also found in wastewater treatment plants.
Occurrences of concrete degradation in these structures have been
recorded in a limited fashion in aeration tanks [15], in septic tanks
and pumping stations [16] and the underside of concrete slabs and
in primary inuent channels [17]. The latter two sources both
make reference to the fact that corrosion has been observed just
above the waterline. This is signicant in that prior experimental
research [5,18] into understanding degradation of concrete in sewer pipes has proven that optimum corrosion levels also occur just
above the waterline. Work carried out into determining depth proles of sulfate ingress into concrete noted that core samples were
taken from the walls surrounding the spiral pump of a sewage
treatment plant as well as the concrete walls of a clarier which
has been damaged by sulfates originating from the sewage waters
[19].
Evidence thus far has identied bacterial manifestation of the
genus Thiobacillus as a major contributor to the deterioration process of concrete sewer pipelines [5,11]. The product of their metabolism results in sulfuric acid being formed which attacks the
cementitious matrix of the concrete causing loss of strength and
cohesion. Thiobacillus however, plays only a part of a much broader
and complicated corrosion process. In the often anaerobic conditions which develop in raw sewage inuent, sulfate-reducing bacteria convert sulfates into suldes such as hydrogen sulde (H2S)
gas. In favourable conditions this diffuses into the atmosphere
and, in the presence of oxygen, is further reduced to elemental sulfur or partially reduced sulfur compounds. In turn, they provide the
catalyst necessary for the aerobic Thiobacillus bacteria to begin producing sulfuric acid; a more detailed explanation of the corrosion
process is presented in a subsequent section.
Sulfuric acid has been identied as a corrosive agent not only in
corroding sewers but also in wastewater treatment plants [20,21].
An attack by sulfuric acid however is a combined acidsulfate reaction with the hydrogen ion causing a dissolution effect, coupled
with corrosive role played by the sulfate ion [2,22]. When sulfuric
According to Skalny et al. [22], the ettringite can be located in

deeper sections of concrete as long as the pH is high enough for
it to form and the gypsum can migrate into these regions. The evidence gathered by Davis et al. [23] in their analysis of piping, however, showed that little ettringite was discovered in the corroding
front and that the thermodynamics of the conversion to gypsum
may be so fast that ettringite is a short-lived intermediate.
From the evidence discussed above there seems to be a distinct
relationship between the corrosion occurring in concrete sewers
and that in wastewater treatment facilities. Common variables include environmental conditions, the nature of the attack and the
physical results of the attack on the concrete. Mehta and Burrows
[24] have discussed how a paradigm shift is required in concrete
design, moving away from the traditional prescriptive approach
to one that promotes a performance-based design. However for
such an approach to succeed, it is imperative that the deterioration
mechanism is fully understood. In this light it is necessary to account for the severe environments that wastewater infrastructures
will encounter in service, and to take an in-depth look at the current state of research into sulfate and sulfuric acid corrosion in a
wastewater environment.
3. Biodegradation aspects
3.1. Providing resistance to biochemical attack
When assessing the available scientic research, it is important
to consider sulfate attack, sulfuric acid attack and how they are
both relevant in determining the resistance of current concrete design specications to such attacks as biogenic sulfuric acid (BSA)
corrosion. As expected there is much conicting data available on
the subject, a scenario which is eloquently detailed in one practicing engineers publication on the topic [6]. Also of interest is the
performance of cements containing additions of ground granulated
blast-furnace slag (GGBS) which, when mixed with Portland cement, has been proven to possess an inherent sulfate resisting
capability [25,26]. GGBS is being used in increasing quantities in
concrete practice today along with other secondary cementitious
materials (SCMs) such as pulverised fuel ash (PFA). With the high
CO2 emissions associated with the production of Portland cement,
these SCMs have the advantage of being by-products from other
industrial processes and as such can help reduce the CO2 footprint
of a construction project. While concretes produced using these
binders are more dense and durable in the long term, they are also
prone to reduced early age strengths and require particular attention when curing [2729].
In assessing experimental test methods previously used by
researchers many contrasting opinions exist [4,30], including the
proposed inadequacy of sulfate testing as a method to analyse biological corrosion in a wastewater environment while others stipulate simultaneous biological and chemical sulfuric acid testing as
the only true methodology [4]. The participation of the sulfate ion
in sulfuric acid (H2SO4) corrosion and that of residual sulfates present in wastewater (found in efuent from food and beverage
industries [31]) cannot be ignored however. Reviewing in situ
and simulated experimental test methods also provides a valuable
insight into the aggressive nature of the environment that sewers
and wastewater treatment plants are exposed to. This also helps
to characterise the environmental conditions favourable to the
initiation of biogenic sulfuric acid corrosion, allowing scope for
investigating the role played by both sulfate-reducing and sulfuroxidising bacteria.
3.2. Sulfate-reducing bacteria

Initiating the bacterial processes, sulfates present in the raw
sewage in sewer system are converted into suldes by sulfatereducing anaerobic bacteria such as Desulfovibrio [4]. In partially
lled sewers, anaerobic conditions can only occur in the slime
layer on the walls of the pipe above the water line. Some of the
essential environmental conditions necessary in the wastewater
environment for these bacteria to function and grow are dissolved
oxygen levels approaching zero and sufcient carbon and sulfate
concentrations in the wastewater itself [32]. When this occurs they
utilise the sulfates present in the wastewater to obtain the oxygen
they require and in turn release sulfur ions [33]. According to research aimed at quantifying microbial-induced deterioration of
concrete, the bacteria derive the energy required for the reduction
of sulfate by the oxidation of organic compounds and H2 [14]. In
their assessment of Lebanons sewer network, Ayoub et al. [8]
claim that sulfate to sulde reduction takes place when the bacteria derive their oxygen from dissolved oxygen and nitrates in the
wastewater. They state however, that corrosion in Lebanons sewers was not observed to have occurred in areas where dissolved
oxygen levels were greater than zero. If sulfate-reducing bacteria
require dissolved oxygen to induce the corrosion cycle, as they suggest, one must ask why is it that no corrosion was found where dissolved oxygen exists. Their own search of existing literature
suggested that sulde build-up could not occur with dissolved oxygen levels greater than 0.5 mg/l whereas Hewayde et al. [33] set a
level of 0.1 mg/l above which corrosion will not occur.
The nal process in the initial stage of concrete deterioration involves the sulfur ions released by the bacteria. These in turn react
with dissolved hydrogen in the wastewater to form an essential
contributory product in the corrosion process, hydrogen sulde
(H2S) [33]. The hydrogen sulde initially formed is found in its dissolved liquid form but for this poorly soluble compound to contribute to the concrete deterioration process it must leave the
wastewater and enter a gaseous phase. The normal pH of sewage
is slightly acidic and in the range pH 56 but when this begins to
lower in conjunction with turbulent water (often found in sewer
pipes or associated with some wastewater treatment processes),
the H2S escapes and collects in the atmosphere above the water level [4,16,33]. A thin layer of moisture exists on the surface of the
concrete pipe exposed to the atmosphere and it is into here the
hydrogen sulde is gas is dissolved. The condensate layer has a
high pH attributed to the alkalinity of the concrete (which can have
a pH of between 11 and 13). It also serves as the driving force behind the gas dissolution. At high pH levels the hydrogen sulde is
separated into HS or S2 ions which attract more H2S into the
moisture layer [14]. Research has also shown that the concentration of H2S in the moisture lm increases as the pH of the mortar
lining of the concrete pipe decreases [13]. In the presence of oxygen the H2S reacts to form elemental sulfur or partially oxidised
sulfur species [4,9,14,21], which can sometimes be seen in the corrosion products deposited on the concrete surface [18].
481
3.3. Sulfur-oxidising bacteria

The formation of sulfur is perhaps the critical link in the chain of
events leading to the corrosion of concrete in a wastewater environment. In microbiological experiments carried out in 1945 to
investigate why sewer pipes were corroding, Parker [11] discovered ve strains of the species Thiobacillus on the surface of concrete which oxidise sulfur, or some partially reduced form of
sulfur, to form sulfuric acid. More recent research suggests some
of the Thiobacillus strains involved in concrete corrosion as being
Thiobacillus thiooxidans, Thiobacillus intermedius, Thiobacillus perometabolis, Thiobacillus novellus, Thiobacillus thioparus, Thiobacillus
neapolitanus and Thiobacillus versutus all of which are known to oxidize and grow with reduced inorganic sulfur compounds [14,34].
Research has also identied iron-oxidising bacteria, such as Thiobacillus ferrooxidans, as being involved in the production of sulfuric
acid in pyritic ground and in sewage treatment plants [35,36].
Bacteria of the genus Thiobacillus do not attach themselves to
the surface of concrete under any conditions. Roberts et al. [14]
state that the pH of the concrete has to be reduced to 9 and assuming sufcient moisture, nutrients and oxygen are present only then
will the Thiobacillus bacteria colonise. Several theories for the lowering of the pH of the concrete to around 9 have been put forward,
including the involvement of the dissociation process of hydrogen
sulde as discussed above. However the most widely assumed theory is that the pH will be lowered due to the effects of carbonation
[13,14,23]. As a result of in situ tests conducted in a sewage system
with high concentrations of hydrogen sulde (>600 ppm) an alternative theory has been put forward into determining the conditions necessary for bacterial colonisation [7]. The authors claim
that the generally accepted role of carbonation in lowering the
pH of a concretes surface does not hold for their experiments. Instead they theorise that in the thin moisture layer itself, the bacteria oxidise the hydrogen sulde gas to form sulfuric acid, thereby
reducing its pH. They further claim that the bacteria will grow in
the layer even when the pH of the concrete itself ranges from pH
1113. Parker [37] noted in his experimental observations however, that Thiobacillus concretivorus (as he termed the strain of Thiobacillus found to attack concrete) did not convert the hydrogen
sulde directly into sulfuric acid but only free sulfur or other forms
of utilisable sulfur compounds including thiosulfate [38]. In characterising the strain T. thiooxidans, Waksman and Joffe [39] and
Nica et al. [38] also stated that hydrogen sulde and other suldes
are not used directly by the sulfur-oxidising organism.
In recognising the wide range of Thiobacillus strains that take
part in sulfuric acid production, it must be noted that not all thrive
in an identical environment. Some of these strains are categorised
into acid-preferring acidophilic sulfur-oxidising microorganisms
(ASOM), such as T. thiooxidans and neutral-preferring neutrophilic
sulfur-oxidising microorganisms (NSOM), such as T. intermedius
[14,38]. It is proposed that different strains of neutrophilic bacteria
colonise the surface of the concrete as its pH depresses from
approximately a value of 8 to around a value of 6 through their
production of sulfuric acid [23]. It was also found that microbial
succession is a surface phenomenon and that the ASOM move into
the corroding concrete with the corroding layer whereas NSOM do
not.
Parker [11] observed that the bacteria which he was cultivating
survived to a pH of approximately 6.5 above which none was capable of growth. At these slightly acidic pH values the acidophilic sulfur-oxidising bacteria colonise and further depress the pH of the
concrete surface to as low as 2 at which level the strain T. thiooxidans can be found thriving [18,40]. The optimum temperature at
which the acid was produced in its highest quantities after 50 days
was found to be 30 C while Barbosa et al. [15] noted in their research that sulde oxidation by the strain T. dentricans decreased
482
at low temperature and was inhibited at 15.6 C. Parker [11] also

discovered that the rate of acid production in his bacteria increased
with increasing nitrogen levels up to a concentration of 50 ppm,
above which there appeared to be a slight inhibition.
3.4. Other acids and organisms
In a departure from the accepted role of the species Thiobacillus
in lowering the surface pH of concrete from approximately 8 to 4,
some authors have also attributed the initial reduction to that of
fungus growth [5,41]. Mori et al. [5] found an unidentied green
fungus which grew at high pH levels and was capable of reducing
the pH to levels suitable for colonisation and growth of T. thiooxidans. Gu et al. [41] go further in their explanation and identied
the fungus they observed as Fusarium. They claim that this has a
more detrimental effect on the concrete that that of the neutrophilic bacteria T. intermedius. In their research they described the
latter as being able to etch the surface of the concrete while the
fungus Fusarium was able to penetrate the material. They also state
that a wide range of acids are produced by fungi including acetic,
oxalic and glucuronic acids. A further set of experiments [42] using
mortar inoculated with bacteria including T. intermedius was conducted independently of Mori et al. [5]. In these experiments the
deterioration of concrete was thought to be caused by the sulfuric
acid produced by the bacteria; however the authors noted little
gypsum and limited change in the sulfate ion concentration of
the culture medium. They concluded that primary deterioration
of the concrete was caused by carbonic and organic acids, which
include acetic acid which are all metabolites produced by bacteria.
4. The role of biogenic sulfuric acid corrosion
4.1. Attack mechanisms
Only limited work has been carried out in assessing the performance of concrete mixes in a biological environment [4] a surprising fact considering several researchers have claimed that biogenic
sulfuric acid corrosion found in wastewater systems is more severe
than chemical sulfuric acid and sulfate attack [43,44]. This represents a key knowledge gap in the development of a material based
performance specication. While research has identied gypsum,
ettringite and even thaumasite as the end-product of the corrosion
product the debate centres on the order of their formation, their
quantities and specic effects on the cement matrix.
The corrosive nature of a sulfuric acid attack has been well documented from both in situ observations and chemical testing on
concrete [4,5,22,30,4547]. The dissolution effect of the hydrogen
ion and the separate effect of the sulfate ion combine to create
an aggressive set of chemical reactions, threatening the stability
of a cement matrix. Debate exists however regarding the mechanisms behind chemical and biological sulfuric acid attacks, and
resistance to the former does not necessarily result in resistance
to the latter [4,9,48]. Explanations centre on the involvement of
the sulfuric acid producing bacteria Thiobacillus where Monteny
et al. [4] claim that it is the moist conditions in the gypsum corrosion front that constitute an excellent breeding ground for the bacteria to thrive. They then migrate into the concrete producing acid
much closer to the corrosion front although Yamanka et al. [7] dispute this claiming it is the acid itself moving inward. In a chemical
attack however, the poor penetration of sulfuric acid limits the effects of corrosion to the surface [49]. The acid must negotiate its
way through this corrosion layer in order for the attack to continue. It is generally assumed that this results in less severe consequences relative to a biological attack, as the corroded surface acts
as a barrier for further penetration. Hence regular brushing of
loosely adhering particles may be important in any attempt to mimic biological activity with chemical testing [4,50].
4.2. Types of sulfuric acid attack
In 1945, C.D. Parker described a sulfuric acid attack on concrete
sewers as producing a white putty-like deposit, moist, aky and
easily removed from the surface [11,37]. The calcium sulfate (gypsum) formed was a result of a reaction between the hydration products in the cement matrix and the sulfuric acid [22], as previously
described in Eq. (1). Experimental and in situ analysis of both mortar and concrete has conrmed that gypsum formation is one of the
primary corrosion mechanisms involved in the deterioration of the
cement matrix leading to a loss of cohesion in cementitious calcium
compounds [5,23,33,51]. The degradation of concrete foundations
of an Italian building exposed to sewage waters however was
attributed to the growth of gypsum crystals at the aggregate-paste
interface causing a loss of strength [52]. The build-up of gypsum
though can also act as a barrier to further penetration, slowing an
attack [4,53] however it has also been claimed that the rougher surface area leads to a greater surface area to be attacked [18].
The relative resistance of various binder combinations to sulfuric acid attack has been discussed by some researchers. Experiments exposing 100 mm Portland cement concrete cubes with a
binder of 35% ordinary Portland cement (OPC)/65% GGBS to an
H2SO4 solution for 5 months, as described in BRE Digest 363 [54],
reported higher performance than for binders of 100% sulfate
resisting Portland cement (SRPC) or 75% OPC/25% PFA [47]. This
improved performance of concrete in acidic conditions has been
attributed to either lower porosity, lower levels of calcium hydroxide or both [4,45,48] while Saricimen et al. [16] determined that in
a 3% owing H2SO4 solution neither SRPC nor OPC showed any difference in resisting attack, a conclusion supported by [7]. Monteny
et al. [43] suggest that a rened pore structure will increase the
capillary action of the cement matrix and act as a mechanism for
the aggressive solution to nd its way deeper into the concrete.
In experiments to assess commercially available piping, De Belie et al. [9] prepared non-standard cylindrical specimens of concrete with CEM I and CEM III high sulfate resisting cement and
exposed them to a 0.5% H2SO4 solution in alternating wet/dry cycles. They concluded the limestone aggregate, acting as a sacricial
medium to reduce the rate of acid attack, played a more crucial
role against attack that the cement type. The sulfate resisting cements also performed better than the blast-furnace slag cements,
an observation similarly supported by other experimental results
[29] (conducting experiments with 60% GGBS cylinders in a 1%
H2SO4 for 168 days). This is however contradicted by research from
Monteny et al. [4] who performed experiments in 15% H2SO4
solutions. However it is noteworthy that the signicance of the role
played by the limestone aggregate has been emphasised [25,29].
Ettringite is a crystalline compound and its formation can be
observed in the process of cement hydration (primary ettringite)
and in the effects of an external sulfate attack (secondary ettringite). Some of the reactions associated with its formation involve
calcium aluminates, such as C3A, and gypsum but may also incorporate an external sulfate attack on the calcium aluminate hydrates and monosulfate hydrate phases [4,54]. According to
Skalny et al. [22] under sulfuric acid attack only limited amounts
of ettringite will form in deeper sections of the concrete as long
as the pH is high enough to maintain its stability and enough of
the gypsum formed in the initial stages of attack can move into
the concrete. This assessment concurs with other researchers
who have also stated ettringites inability to survive in an acidic
environment [44] and even in alkaline environments with pHs
as high as 10.6 [49]. In contrast, Monteny et al. [4] stress in their
assessments the importance of ettringite and its more devastating
effect on concrete than gypsum, while its formation from a sulfuric

acid attack was also documented by others assessing the inuence
of fungi on concrete corrosion [42] and simulated biogenic sulfuric
acid corrosion [5].
It is noteworthy that the presence of such key compounds such
as gypsum and ettringite is accepted as being a function of mix design and the binder combinations used. However the notion of
using this material design to control the presence of these expansive compounds is not at this stage well developed.
4.3. Inuence of the sulfate ion
As an attack by sulfuric acid is a combined acidsulfate reaction,
many researchers have deemed it prudent to assess concrete susceptibility in standard sulfate testing solutions including sodium
sulfate (Na2SO4), magnesium sulfate (MgSO4) or a combination of
both. The validity of this method to assess attack in a wastewater
environment has however drawn some uncertainty based on discrepancies in chemical and biological tests [4].
Sodium and magnesium-based sulfate solutions have substantially different effects on concrete. With the former, calcium
hydroxide primarily undergoes decomposition to gypsum and subsequently ettringite. When there is an insufcient source of calcium for the reaction to continue only then will the solution
begin to attack the CSH phase [22,51]. Magnesium solutions attack all phases simultaneously in the cement matrix preferring calcium hydroxide rst followed by the calciumsilicatehydrate (C
SH) phase to obtain its reactive calcium. The products from a
magnesium sulfate reaction include gypsum, ettringite, a magnesiumsilicatehydrate (which lacks cohesive properties) and the
mineral form of magnesium hydroxide, brucite [55].
In sodium sulfate, ettringite can be associated mainly with the
reaction between the AFm monosulfate phase and the sulfate ions
migrating into the concrete. At low concentrations of sulfate solutions (<1000 mg SO2
4 /l) ettringite will be the primary cause of
deterioration [4] whereas at higher concentrations (>8000 mg
SO2
4 /l) gypsum will dominate in a sulfate attack [56]. It is important, therefore, to use a concentration of sulfates that accurately
represents the corrosion mechanism in the desired environment.
In magnesium sulfate solutions the deterioration mechanism is
primarily a result of the loss of cohesion and disintegration with
the formation of gypsum and magnesium hydroxide [4,22]. The
saturated solution pH of magnesium hydroxide is approximately
10.5 and consequently this causes the destabilisation of ettringite.
As a result the circumstances favourable in the formation of
ettringite from a magnesium sulfate attack are signicantly impeded [57]. Skalny et al. [22] do note however that a limited
amount may form when the pH remains high enough in the concrete for a sufcient period of time while research on slag cements
[58] attributed ettringite formation as substantially contributing to
the damage produced by MgSO4 solutions.
Gollop and Taylor [51,58] concluded in their analysis that the
resistance of GGBS concretes to attack by sulfates increases with
decreasing levels of Al2O3. Lower levels of C3A were noted by other
researchers [16,29] in reducing the harmful effects of exposure to
sodium sulfate. In using cement pastes in their analysis however,
Gollop and Taylor neglected the effects of the aggregate-paste
interface previously considered important in analysing a sulfate/
sulfuric acid attack [49,5961]. Their addition of increasing levels
of GGBS up to a level of 92% increased resistance to attack by sodium sulfate solutions but had the opposite effect when exposed
to magnesium sulfate. In an assessment of 150 mm 75 mm reinforced concrete cylinder specimens exposed to a 2.1% SO2
4 sulfate
solution, Al-Amoudi [61] indicated that for a 60% GGBS replacement level, deterioration in the mixed magnesium/sodium based
solution was considered signicant. It was concluded that GGBS
483
mixes fared poorest when compared to other cement replacement

materials including silica fume (10% replacement) and y ash (20%
replacement). In assessing results from a study by the BRE [25,46],
Osborne [29] also came to similar conclusions regarding the effects
of magnesium and sodium sulfate solutions and the use of high
percentages of GGBS as a cement replacement. The TEG one-year
review [62] also noted the benet of a 70% GGBS replacement level
with limestone cement and good quality carbonate aggregate
against conventional forms of sulfate attack.
4.4. Simulation of the biological corrosion process
In a simulated wet/dry 17-day attack cycle Vincke et al. [21] exposed 2 2 5 cm specimens of concrete to a biological sulfur
solution containing Thiobacilli bacteria following an incubation
period in an H2S environment. After a total of 51 days and three cycles, the specimens made with a CEM I Portland cement and CEM
III blast-furnace slag cement were analysed in terms of weight loss.
Results indicated that both mixes performed similarly. De Belie
et al. [9] used an almost identical process to the above [21], using
specimens that were 80 mm diameter and 15 mm deep, which
were subjected to a fourth cycle of 17 days. In their experiments
they observed the sulfate ion concentration of their solution to increase from 2 g/l to 4 g/l which the authors cite as evidence for the
production of sulfuric acid by the sulfur-oxidising bacteria. The results of their experiments concluded that Portland cement performed better than CEM III blast-furnace slag cement. In this
instance they theorise that owing to the greater surface area of
CEM III the bacteria are able to colonise the surface of the cement
more rapidly than the Portland cement.
Further investigation has revealed other methods of modelling
biological corrosion in the wastewater environment. A simulation
chamber was developed by researchers in Hamburg, described by
Monteny et al. [4], which allowed the corrosion process to be modelled at eight times the in situ level could be reached through the
optimisation of the corrosive environment. Test blocks of
60 11 7 cm were immersed in 10 cm of water at 30 C and
sprayed with Thiobacilli bacteria. H2S gas at 10 ppmv was pumped
into the chamber and acted as a substrate for the bacteria. The
number of bacteria on the surface of the specimens was counted
and it was found that the rate of corrosion was dependent on the
levels of T. thiooxidans detected.
Experimental work was also carried out into the corrosion
mechanism involved in the deterioration of concrete constructing
a simulated sewer pipe 20 m long and a diameter of 15 cm [5]. Test
specimens of mortar bars 4 4 16 cm were made with the bottom half of these bars placed in sewage and exposed to H2S gas not
exceeding 300 ppm. Identical mortar bars were placed half submersed into a sewage medium, an autotrophic basal growth culture medium without thiosulfate and distilled water. These were
inoculated every two weeks with T. thiooxidans. Corrosion just
above the waterline was observed on bars in the sewage and autotrophic basal media. Those in water remained unaffected while the
sewage samples displayed the greatest corrosion rate. The authors
concluded that based on these results the bacteria required a supply of moisture and nutrients to initiate the corrosion process
while the corrosion products formed were determined to be gypsum and secondary ettringite. As with the issue of sulfuric acid attack, the possibility of restricting the formation of corrosion
products through appropriate mix design is not developed.
5. Conclusions
Three research foci were evident in the study of sulfate/sulfuric
acid effects on concrete. These are:
484
Studies of the biological processes behind the corrosion of

wastewater infrastructure, with particular reference to the role
of sulfate-reducing and sulfur-oxidising bacteria.
Studies of the chemical effects of sulfates and sulfuric acid on
concrete mixes.
Laboratory-based research methodologies, especially those
incorporating the biological effect on concrete.
Chemical tests alone do not fully represent the microbial effects
on concrete, although they may help in assessing the types of
damage that can occur. Some researchers have carried out fullscale laboratory analysis, but it is worth noting that the equipment
necessary to adequately mimic in situ conditions is invariably
complicated, cumbersome and custom built [4,63]. The realisation
of resources required to undertake such research continues to be
an obstacle to addressing this topic. The use of such complex
research apparatus in routine performance-based specication is
impractical.
Although there exists signicant quantities of data on the topics
of sulfate, sulfuric acid and biogenic corrosion of concrete, little has
been achieved in the way of formulating an accepted mathematical
model of deterioration that incorporates agreed parameters of signicance. This represents a signicant knowledge gap and acts as a
technical barrier towards using material design as a means of controlling corrosion due to biochemical attack. This continues to inhibit the design of durable concrete wastewater infrastructure and
has signicant implications for public expenditure in this area.
The need to consider the interaction of biological and chemical
processes may hold the key to achieving greater progress and allow
practitioners to use concrete mix design as a means of delivering
intended service lives.
Acknowledgements
The authors gratefully acknowledge the nancial support provided by Enterprise Ireland Innovation Partnership Project IP/
2008/540 and Ecocem Ireland.
References
[1] Congressional budget ofce. future investment in drinking and wastewater
infrastructure. ISBN 0160512433, Congressional Budget Ofce; 2002.
[2] Attiogbe EK, Rizkalla SH. Response of concrete to sulfuric acid attack. ACI Mater
J 1988;84(6):4818.
[3] Beeldens A, Monteny J, Vincke E, De Belie N, Van Gemert D, Taerwe L, et al.
Resistance to biogenic sulfuric acid corrosion of polymer-modied mortars.
Cem Concr Compos 2001;23(1):4756.
[4] Monteny J, Vincke E, Beeldens A, De Belie N, Taerwe L, Van Gemert D, et al.
Chemical, microbiological, and in situ test methods for biogenic sulfuric acid
corrosion of concrete. Cem Concr Res 2000;30(4):62334.
[5] Mori T, Nonaka T, Tazaki K, Koga M, Hikosaka Y, Noda S. Interactions of
nutrients, moisture and pH on microbial corrosion of concrete sewer pipes.
Water Res 1992;26(1):2937.
[6] Neville A. The confused world of sulfate attack on concrete. Cem Concr Res
2004;34(8):127596.
[7] Yamanaka T, Aso I, Togashi S, Tanigawa M, Shoji K, Watanabe T, et al. Corrosion
by bacteria of concrete in sewerage systems and inhibitory effects of formates
on their growth. Water Res 2002;36(10):263642.
[8] Ayoub GM, Azar N, El Fadel M, Hamad B. Assessment of hydrogen sulde
corrosion of cementitious sewer pipes: a case study. Urban Water J
2004;1(1):3953.
[9] De Belie N, Monteny J, Beeldens A, Vincke E, Van Gemert D, Verstraete W.
Experimental research and prediction of the effect of chemical and biogenic
sulfuric acid on different types of commercially produced concrete sewer
pipes. Cem Concr Res 2004;34(12):222336.
[10] Kawamura S. Integrated design and operation of water treatment
facilities. Wiley; 2000.
[11] Parker CD. The isolation of a species of bacterium associated with the
corrosion of concrete exposed to atmospheres containing hydrogen sulde.
Aust J Exp Biol Med Sci 1945;23:8190.
[12] Fan CY, Field R, Pisano WC, Barsanti J, Joyce JJ, Sorenson H. Sewer and tank
ushing for sediment, corrosion, and pollution control. J Water Res Pl
2001;127(3):1946.
[13] Jana D, Lewis RA. Acid attack in a concrete sewer pipe a petrographic and
chemical investigation. In: Proceedings of 27th international conference on
cement microscopy. Victoria, Canada; 2005.
[14] Roberts DJ, Nica D, Zuo G, Davis JL. Quantifying microbially induced
deterioration of concrete: initial studies. Int Biodeter Biodegr
2002;49(4):22734.
[15] Barbosa VL, Burgess JE, Darke K, Stuetz RM. Activated sludge biotreatment of
sulphurous waste emissions. Rev Env Sci Biotech 2002;1(4):34562.
[16] Saricimen H, Shameem M, Barry MS, Ibrahim M, Abbasi TA. Durability of
proprietary cementitious materials for use in wastewater transport systems.
Cem Concr Compos 2003;25(4):4217.
[17] Stufebean J. Report on bids and award of contract for the San Jos/Santa Clara
water pollution control plant, FY 2007/2008 CIP, east primary inuent channel
repair project. San Jos, California; 2007.
[18] Vollertsen J, Nielsen AH, Jensen HS, Wium-Andersen T, Hvitved-Jacobsen T.
Corrosion of concrete sewers the kinetics of hydrogen sulde oxidation. Sci
Total Environ 2008;394(1):16270.
[19] Weritz F, Taffe A, Schaurich D, Wilsch G. Detailed depth proles of sulfate
ingress into concrete measured with laser induced breakdown spectroscopy.
Constr Build Mater 2009;23(1):27583.
[20] Idriss AF, Negi SC, Jofriet JC, Hayward GL. Corrosion of steel reinforcement in
mortar specimens exposed to hydrogen sulde, part 1: impressed voltage and
electrochemical potential tests. J Agr Eng Res 2001;79(3):22330.
[21] Vincke E, Verstichel S, Monteny J, Verstraete W. A new test procedure
for biogenic sulfuric acid corrosion of concrete. Biodegradation 1999;10(6):
4218.
[22] Skalny J, Marchand J, Odler I. Sulfate attack on concrete. London: Spon Press;
2002.
[23] Davis JL, Nica D, Shields K, Roberts DJ. Analysis of concrete from corroded
sewer pipe. Int Biodeter Biodegr 1998;42(1):7584.
[24] Mehta PK, Burrows RW. Building durable structures in the 21st century. Concr
Int 2001;23(3):5763.
[25] Building Research Establishment. BRE special digest 1, concrete in aggressive
ground: part 1: assessing the aggressive chemical environment, 2nd ed.; 2003.
[26] Higgins DD. Increased sulfate resistance of GGBS concrete in the presence of
carbonate. Cem Concr Compos 2003;25(8):9139.
[27] Chidiac SE, Panesar DK. Evolution of mechanical properties of concrete
containing ground granulated blast furnace slag and effects on the scaling
resistance test at 28 days. Cem Concr Compos 2008;30(2):6371.
[28] McNally C, Richardson MG, Evans C, Callanan T. Determination of chloride
diffusion coefcients for use with performance-based specications. In: Dhir
RK, Newlands MD, Whyte A, editors. Proceedings of 6th international congress
global construction: ultimate concrete opportunities; application of codes,
designs and regulations. Dundee; 2005. p. 3217.
[29] Osborne GJ. Durability of Portland blast-furnace slag cement concrete. Cem
Concr Compos 1999;21(1):1121.
[30] Chang ZT, Song XJ, Munn R, Marosszeky M. Using limestone aggregates and
different cements for enhancing resistance of concrete to sulfuric acid attack.
Cem Concr Res 2005;35(8):148694.
[31] Percheron G, Bernet N, Moletta R. Start-up of anaerobic digestion of sulfate
wastewater. Bioresour Technol 1997;61(1):217.
[32] Mohan SV, Rao NC, Prasad KK, Sarma PN. Bioaugmentation of an anaerobic
sequencing batch biolm reactor (AnSBBR) with immobilized sulphate
reducing bacteria (SRB) for the treatment of sulphate bearing chemical
wastewater. Process Biochem 2005;40(8):284957.
[33] Hewayde E, Nehdi M, Allouche E, Nakhla G. Effect of geopolymer cement on
microstructure, compressive strength and sulfuric acid resistance of concrete.
Mag Concr Res 2006;58(5):32131.
[34] Emtiazi G, Habibi MH, Setareh M. Isolation of some new sulphur bacteria from
activated sludge. J Appl Microbiol 1990;69(6):86470.
[35] Longworth TI. Contribution of construction activity to aggressive ground
conditions causing the thaumasite form of sulfate attack to concrete in pyritic
ground. Cem Concr Compos 2003;25(8):100513.
[36] Maeda T, Negishi A, Komoto H, Oshima Y, Kamimura K, Sugio T. Isolation of
iron-oxidizing bacteria from corroded concretes of sewage treatment plants. J
Biosci Bioeng 1999;88(3):3005.
[37] Parker CD. The function of Thiobacillus concretivorus (nov. spec.) in the
corrosion of concrete exposed to atmospheres containing hydrogen sulde.
Aust J Exp Biol Med Sci 1945;23:918.
[38] Nica D, Davis JL, Kirby L, Zuo G, Roberts DJ. Isolation and characterization of
microorganisms involved in the biodeterioration of concrete in sewers. Int
Biodeter Biodegr 2000;46(1):618.
[39] Waksman SA, Joffe JS. Microorganisms concerned in the oxidation of sulfur in
the soil II. Thiobacillus thiooxidans, a new sulfur-oxidizing organism isolated
from the soil. J Bacteriol 1922;7:23956.
[40] Jin SM, Yan WM, Wang ZN. Transfer of IncP plasmids to extremely acidophilic
Thiobacillus thiooxidans. Appl Environ Microbiol 1992;58(1):42930.
[41] Gu JD, Ford TE, Berke NS, Mitchell R. Biodeterioration of concrete by the fungus
Fusarium. Int Biodeter Biodegr 1998;41(2):1019.
[42] Tazawa EI, Morinaga T, Kawai K. Deterioration of concrete derived from
metabolites of microorganisms. In: Proceedings 3rd CANMET/ACI international
conference durability of concrete. American Concrete Institute. Nice, France;
1994. p. 108797.
[43] Monteny J, De Belie N, Vincke E, Verstraete W, Taerwe L. Chemical and
microbiological tests to simulate sulfuric acid corrosion of polymer-modied
concrete. Cem Concr Res 2001;31(9):135965.

[44] Thomson G. Corrosion and rehabilitation of concrete access/inspection
chambers. In: Proceedings of 63rd annual water industry engineers and
operators conference. Brauer College, Warrnambool, Australia; 2000. p. 2835.
[45] Bassuoni MT, Nehdi ML. Resistance of self-consolidating concrete to sulfuric
acid attack with consecutive pH reduction. Cem Concr Res 2007;37(7):
107084.
[46] Building Research Establishment. BRE special digest 1, concrete in aggressive
ground. Part 2: specifying the concrete and additional protective measures,
2nd ed.; 2003.
[47] Hill J, Byars EA, Sharp JH, Lynsdale CJ, Cripps JC, Zhou Q. An experimental study
of combined acid and sulfate attack of concrete. Cem Concr Compos
2003;25(8):9971003.
[48] Vincke E, Wanseele EV, Monteny J, Beeldens A, Belie ND, Taerwe L, et al.
Inuence of polymer addition on biogenic sulfuric acid attack of concrete. Int
Biodeter Biodegr 2002;49(4):28392.
[49] Allahverdi A, Skvara F. Acidic corrosion of hydrated cement based materials.
Part 2 kinetics of the phenomenon and mathematical models. Ceram
Silikty 2000;44(4):15260.
[50] De Belie N. Evaluation of methods for testing concrete degradation in
aggressive solutions. In: Proceedings of workshop on performance of
cement-based materials in aggressive aqueous environments
characterisation, modelling, test methods and engineering aspects. RILEM
Publications SARL; 2008. p. 7990.
[51] Gollop RS, Taylor HFW. Microstructural and microanalytical studies of sulfate
attack. IV. Reactions of a slag cement paste with sodium and magnesium
sulfate solutions. Cem Concr Res 1996;26(7):101328.
[52] Tulliani JM, Montanaro L, Negro A, Collepardi M. Sulfate attack of concrete
building foundations induced by sewage waters. Cem Concr Res 2002;32(6):
8439.
485
[53] Rendell F, Jauberthie R. The deterioration of mortar in sulphate environments.

Constr Build Mater 1999;13(6):3217.
[54] Building Research Establishment. BRE digest 363, sulfate and acid resistance of
concrete in the ground, 2nd ed.; 1991.
[55] Collepardi MA. State-of-the-art review on delayed ettringite attack on
concrete. Cem Concr Compos 2003;25(4):4017.
[56] Hekal EE, Kishar E, Mostafa H. Magnesium sulfate attack on hardened blended
cement pastes under different circumstances. Cem Concr Res 2002;32(9):
14217.
[57] Santhanam M, Cohen MD, Olek J. Sulfate attack research whither now? Cem
Concr Res 2001;31(6):84551.
[58] Gollop RS, Taylor HFW. Microstructural and microanalytical studies of sulfate
attack. V. Comparison of different slag blends. Cem Concr Res 1996;26(7):
102944.
[59] Irassar EF, Bonavetti VL, Gonzlez M. Microstructural study of sulfate attack on
ordinary and limestone Portland cements at ambient temperature. Cem Concr
Res 2003;33(1):3141.
[60] Pava S, Condren E. Study of the durability of OPC versus GGBS concrete on
exposure to silage efuent. J Mater Civil Eng 2008;20(4):31320.
[61] Al-Amoudi OSB. Performance of 15 reinforced concrete mixtures in
magnesiumsodium sulphate environments. Constr Build Mater 1995;9(3):
14958.
[62] Clark LA. Thaumasite expert group one-year review. London: Department of
the Environment, Transport and the Regions; 2000.
[63] De Muynck W, De Belie N, Verstraete W. Effectiveness of admixtures, surface
treatments and antimicrobial compounds against biogenic sulfuric acid
corrosion of concrete. Cem Concr Compos 2009;31(3):16370.
APPENDIX B: Conference Paper

O'Connell, M, McNally, C, Donohue, S, Bonal, J & Richardson, MG. (2009) Assessment of
ultrasonic signals to determine the early age properties of concretes incorporating secondary
cementitious materials. In: Proceedings 15th European Meeting of Environmental and
Engineering Geophysics, Dublin, 7-9 September.
Assessment of ultrasonic signals to determine the early age properties of concretes

incorporating secondary cementitious materials
OConnell, M., McNally, C., Donohue, S., Bonal, J. and Richardson, M.G.
Summary
Secondary cementitious materials (SCMs) such as ground granulated blast-furnace slag
(GGBS) are used in increasing quantities in concrete practice internationally. While these
materials offer benefits such as reduced CO2 and a more dense microstructure, they also have
drawbacks in terms of slower initial gain of strength. There are significant financial
implications associated with this, as it can lead to delays in the construction process. Key to
overcoming this challenge is the development of a methodology to assess the early-age
stiffness development in concretes manufactured using GGBS. This paper presents the results
of a study into the application of ultrasonic sensors to assess the early age concrete stiffness.
A novel wavelet-based approach is used to overcome the difficulties associated with wave
reflections and classical wave theory is used to determine the concrete small-strain stiffness
based on P and S wave velocities. It was found that the results are largely in agreement with
those obtained using standard strength testing, suggesting potential practical applications of
this method.
Near Surface 2009 15th European Meeting of Environmental and Engineering Geophysics
Dublin, Ireland, 7 - 9 September 2009
Introduction
Secondary cementitious materials (SCMs) such as ground granulated blast-furnace slag
(GGBS) and pulverized fuel ash (PFA) are used in increasing quantities in concrete practice
internationally. These materials are derived from industrial by-products and offer the
significant advantages of abating the high CO2 emissions associated with cement
manufacture, while also making the concrete more dense and durable in the long term
(McNally et al, 2005). However a significant drawback is that SCMs can lead to the concrete
being relatively weak in the initial few days after being cast, leading to costly delays in the
construction process. Decisions on construction sites on when such a concrete is sufficiently
strong to resist applied loading are often based on empirical site practices, which can be quite
punitive to SCMs. In this context, the importance of being able to assess non-destructively the
early-age strength and stiffness of concrete with or without SCMs becomes clear. Ultrasonic
sensors have the potential to allow such an assessment, but to date there is no clear approach
available on the characterisation of concrete at early ages.
Materials
The experimental procedure required three concrete mixes to be prepared with a varying
amount of GGBS to be used as a cement replacement. The cement used was a CEM II A-L
Portland-limestone-cement and GGBS was introduced at replacement levels of 0%, 50% and
70%. Details of the mix design are outlined in Table 1. A series of eight 100mm cubes and
eight 100mm x 200mm concrete cylinders were prepared for each mix with a water/binder
ratio of 0.45. These were left to cure at room temperature for 24 hours prior to demoulding
after which they were stored in a water curing tank at 20C for up to 28 days.
3
Quantities (kg/m )
Mix ID
Cement
GGBS
20mm.
10mm.
Sand
Water
MA
360
810
405
685
162
MB
180
180
805
400
680
162
MC
108
252
805
400
162
162
Table 1: Concrete mix designs

Wavelet Analysis of Ultrasonic Signals
It is well known that the Youngs modulus of a material can be determined from the velocity
of the P and S waves across a sample. This approach may be applied using ultrasonic sensors
on concrete samples to allow quantification of the increase in concrete stiffness due to further
hydration of the cementitious materials present. However for this to be done accurately, it is
key that the arrival time of the P and S waves can be determined. For the former this is a
relatively straightforward task as the P-wave arrival can be visually detected from the 1st
discontinuity in the signal. However for the S-wave arrival the situation is less clear, as there
exists a significant amount of interference from the presence of reflected waves off the side
boundaries of the sample. It is in this context that a wavelet-based algorithm was developed to
allow detection of the discontinuity in the signal associated with the S-wave arrival.
A signal may be observed through two main domains: time domain and frequency domain.
The Fourier Transform and its inverse connect these domains and are the main mathematical
tools for signal analysis. The Fourier Transform is perfectly adequate for stationary and
periodic signals and provides a global description of frequency distribution, energy and
overall regularity. However, it involves the complete loss of local time information such as
the location of singularities. A wavelet is a mathematical function used to divide a given
function or continuous-time signal into different frequency components and study each
component with a resolution that matches its scale. A wavelet transform is the representation
of a function by wavelets. The wavelets are scaled and translated copies (known as "daughter
wavelets") of a finite-length or fast-decaying oscillating waveform (known as the "mother
wavelet"). Wavelet transforms have advantages over traditional Fourier transforms for
representing functions that have discontinuities and sharp peaks, and for accurately
deconstructing and reconstructing finite, non-periodic and/or non-stationary signals. The
Wavelet Transform is motivated by the possibility of finding a singularity as it decomposes
the signal into elementary building blocks that are well localized both in time and frequency
(Mallat and Hwang, 1992). The local detail is matched to the scale of the wavelet, so it can
characterise coarse (low frequency) features on large scales and fine (high frequency) features
on small scales.
By assuming the shear wave to be both plane and homogenous, the shear wave arrival in a
bender element test is characterised by the arrival of a broad-band energy. The shear wave is
however preceded by the near-field effect, waves reflecting off the boundaries of the sample
which create a first singular point in the output signal, as illustrated in Fig. 2. It induces an
opposite phase wave preceding the S-wave. The main S-wave arrival creates a second singular
point; however its location in the time domain is usually scrambled by the near-field effect
and the noise. Nevertheless this singularity exists and is defined as a discontinuity in the first
derivative at this time.
Bonal et al. (2008) have presented a novel method of analysing signals using wavelets based
on the Lipschitz exponent (Mallat and Hwang, 1992). The Lipschitz exponent is a well known
tool used to estimate function differentiability. A key feature of the Lipschitz exponent is its
ability to distinguish between singularities due to noise, and those due to events such as the
arrival of the S-wave. In order to accurately determine the first arrival of a shear wave using
wavelets, Bonal et al (2008) followed several maxima lines of the wavelet transform modulus
across a range of scales. The local Lipschitz exponents are determined and the discontinuities
sorted based on this result. They observed the first arrival to be among these singular points
with a local Lipschitz exponent of almost 1; this value is variable but must be compatible with
the characteristics of the input function. This algorithm was then implemented using a Python
script; this approach for wavelet based singularity detection does not give automated results,
but nonetheless directs us to points of interest within the signal.
Methodology
The investigation required S-wave and P-wave ultrasonic readings to be taken on cubes at
one, three, eight, fourteen and twenty-eight days following casting of the specimens. Two sets
of transducers were used for this purpose in conjunction with a square wave pulser-receiver in
through-transmission mode. The S-wave transducers had a frequency of 0.1 MHz, the Pwave transducers 50 kHz. For ultrasonic S-wave measurements each transducer was coupled
directly opposite the other using a shear wave couplant gel. A 100V amplitude pulse was
emitted into the specimen for a duration of two minutes and readings were recorded using a
digital oscilloscope connected to a laptop computer. A similar procedure was used for Pwaves with a P-wave couplant gel. The previously described Python script was now
employed to locate the first S-wave arrival; the application of this script is shown in Fig. 2.
To calculate static Youngs modulus for each mix at eight, fourteen and twenty-eight days
tests were carried out in accordance with BS 1881-121 (1983). Extensometers were used to
determine the mean micro-strain of the cylinder at the upper and basic applied stresses.
Fig 1: Ultrasonic measurement experimental set-up: (L-R: laptop, oscilloscope, pulserreceiver, transducers, 100mm cube and couplant gels)
With the stresses known and the micro-strain readings given by the extensometers, a static
Youngs modulus value to the nearest 100 N/mm2 was calculated for each sample tested.
From ultrasonic testing, the velocity of the P-wave (VP) and the S-wave (VS) can be
calculated. Knowing these, the small strain shear modulus and the Poissons ratio can be
determined from Eqn 1 and 2 respectively. Using these values the small strain Youngs
modulus can then be ascertained (Eqn 3).
Eqn 1
Eqn 2
Eqn 3
Fig. 2: S-wave signal showing singularity detection

using a Python script
Results
The results for the experimental testing programme are shown below in Fig. 3. The trends
observed in small strain Youngs modulus, static Youngs modulus and compressive strength
are broadly in line with what is expected for each of the three concrete mixes. The 70%
GGBS mix is clearly defined as being the slowest to develop strength and stiffness at early
ages, although it can be seen that this does gradually improve over time. The shape of the
curves for strength and small-strain stiffness are also quite similar, giving confidence in the
results produced using the wavelet singularity detection algorithm. The approach also appears
more sensitive than the standard static modulus of elasticity, which suggests very little
difference in the concrete properties, regardless of GGBS content.
Fig. 3: Results of experimental testing programmes

Conclusions
Based on the presented results a number of conclusions can be drawn:
A wavelet-based approach is a valid tool for determining the shear wave velocities in
concrete samples, and is capable of overcoming the issues associated with reflected
waves. However care is needed in determining appropriate Lipschitz exponents.
The small strain Youngs modulus and compressive strengths for early age concrete
follow similar trends for all GGBS contents; the static modulus of elasticity appears
less sensitive to variations in the GGBS.
Ultrasonic sensors have the potential to be used in this application, with potentially
significant savings to companies seeking to use secondary cementitious materials in
concrete practice.
Acknowledgements
The authors would like to acknowledge the financial support of Ecocem Ireland Ltd. and the
Enterprise Ireland Innovation Partnership programme (grant no IP/2008/0540). The assistance
of Mr. Eoin Dunne of Trinity College Dublin is also gratefully acknowledged.
References
Bonal, J., Donohue, S. & McNally, C., (2008) Examination of a novel wavelet-based
approach for bender element testing. In: Cannon, E., West, R. & Fanning, P. eds. Bridge and
Infrastructure Research in Ireland, BRI 2008, Galway, Ireland, pp.435442 .
Mallat, S. and Hwang, W.L., (1992) Singularity detection and processing with wavelets.
Information Theory, IEEE Transactions, Vol. 38 (2) pp.617643, 1992.
McNally, C., Richardson, M.G., Evans, C., & Callanan, T., (2005) Determination of chloride
diffusion coefficients for use with performance-based specifications. Proceedings of the 6th
International Congress on Global Construction: Ultimate Concrete Opportunities;
Application of Codes, Designs and Regulations Dundee, pp.321327.
APPENDIX C: Sodium Sulfate Expansion Data

CEM II-A/L 100%
0.3
Expansion %
0.25
0.2
Prism 1
0.15
Prism 2
0.1
Prism 3
Prism 4
0.05
0
0
56
112
168
224
280
336
392
448
504
560
Days Exposure
Days
0
28
56
84
112
140
175
196
224
252
280
308
336
364
392
420
448
476
504
L (%) P1
0
0
0.006
0.012
0.025
0.027
0.029
0.035
0.043
0.045
0.051
0.06
0.066
0.073
0.081
0.101
0.105
0.119
0.141
L (%)P2
0.000
0.000
0.003
0.007
0.018
0.031
0.029
0.034
0.046
0.053
0.062
0.077
0.090
0.109
0.128
0.154
0.182
0.222
0.268
L (%)P3
0
0.01
0.004
0.01
0.019
0.024
0.026
0.031
0.041
0.046
0.045
0.053
0.058
0.069
0.077
0.093
0.102
0.119
0.138
L (%)P4
0
0.01
0.01
0.016
0.027
0.029
0.031
0.037
0.046
0.047
0.05
0.058
0.062
0.072
0.078
0.092
0.097
0.114
0.131
CEM II-A/L + 50% GGBS

0.04
0.035
Expansion %
0.03
0.025
Prism 1
0.02
Prism 2
0.015
Prism 3
0.01
Prism 4
0.005
0
0
56
112
168
224
280
336
392
448
504
560
Days Exposure
Days
0
28
56
84
112
140
175
196
224
252
280
308
336
364
392
420
448
476
504
L (%)P1
0
0.004
0.006
0.012
0.019
0.015
0.013
0.015
0.017
0.018
0.017
0.018
0.018
0.018
0.021
0.021
0.022
0.026
0.027
L (%)P2
0.000
0.006
0.007
0.012
0.018
0.018
0.016
0.017
0.017
0.020
0.022
0.022
0.024
0.024
0.026
0.028
0.030
0.030
0.032
L (%)P3
0
0.004
0.008
0.009
0.013
0.016
0.015
0.016
0.017
0.017
0.020
0.021
0.022
0.022
0.026
0.025
0.027
0.030
0.030
L (%)P4
0
0.006
0.005
0.011
0.012
0.015
0.019
0.018
0.020
0.021
0.024
0.026
0.026
0.027
0.03
0.031
0.032
0.033
0.035
CEMII-A/L + 70% GGBS

0.04
0.035
Expansion %
0.03
0.025
Prism 1
0.02
Prism 2
0.015
Prism 3
0.01
Prism 4
0.005
0
0
56
112
168
224
280
336
392
448
504
560
Days Exposure
Days
0
28
56
84
112
140
175
196
224
252
280
308
336
364
392
420
448
476
504
L (%)P1
0
0.005
0.004
0.008
0.010
0.013
0.017
0.02
0.019
0.022
0.024
0.026
0.026
0.026
0.029
0.028
0.034
0.033
0.033
L (%)P2
0.000
0.002
0.004
0.010
0.010
0.015
0.012
0.014
0.014
0.017
0.018
0.021
0.020
0.021
0.024
0.026
0.030
0.030
0.031
L (%)P3
0
0.008
0.002
0.012
0.014
0.016
0.015
0.017
0.017
0.020
0.022
0.023
0.023
0.024
0.027
0.027
0.029
0.031
0.035
L (%)P4
0
0.005
0.004
0.012
0.010
0.014
0.014
0.016
0.017
0.019
0.02
0.025
0.023
0.024
0.029
0.027
0.03
0.032
0.036
CEM I 100%
0.8
0.7
Expansion %
0.6
0.5
Prism 1
0.4
Prism 2
0.3
Prism 3
0.2
Prism 4
0.1
0
0
56
112
168
224
280
336
392
448
504
Days Exposure
Days
0
28
56
84
119
140
168
196
224
252
280
308
336
364
392
420
448
L (%)P1
0
0.013
0.025
0.029
0.037
0.048
0.059
0.072
0.088
0.109
0.123
0.153
0.185
0.249
0.309
0.407
0.546
L (%)P2
0.000
0.003
0.015
0.024
0.031
0.043
0.055
0.068
0.084
0.104
0.122
0.153
0.184
0.239
0.297
0.377
0.502
L (%)P3
0
0.008
0.022
0.031
0.041
0.056
0.071
0.086
0.107
0.134
0.162
0.209
0.258
0.341
0.445
0.571
0.725
L (%)P4
0
0.014
0.026
0.034
0.046
0.058
0.072
0.089
0.109
0.132
0.155
0.196
0.236
0.315
0.404
0.52
0.664
CEM I + 70% GGBS

0.06
Expansion %
0.05
0.04
Prism 1
0.03
Prism 2
0.02
Prism 3
Prism 4
0.01
0
0
56
112
168
224
280
336
392
448
504
Days Exposure
Days
0
28
56
84
119
140
168
196
224
252
280
308
336
364
392
420
448
L (%)P1
0
0.003
0.006
0.015
0.013
0.018
0.016
0.019
0.02
0.021
0.023
0.023
0.024
0.028
0.03
0.031
0.033
L (%)P2
0.000
0.008
0.012
0.016
0.017
0.021
0.024
0.026
0.028
0.033
0.034
0.034
0.039
0.041
0.042
0.046
0.049
L (%)P3
0
0
0.006
0.009
0.014
0.017
0.018
0.021
0.023
0.025
0.026
0.028
0.029
0.034
0.034
0.035
0.037
L (%)P4
0
0.002
0.008
0.013
0.021
0.024
0.026
0.028
0.031
0.034
0.036
0.038
0.039
0.042
0.044
0.046
0.047
SRPC 100%
0.08
0.07
Expansion %
0.06
0.05
Prism 1
0.04
Prism 2
0.03
Prism 3
0.02
Prism 4
0.01
0
0
56
112
168
224
280
336
392
448
Days Exposure
Days
0
28
56
84
112
140
168
196
224
252
280
308
336
364
392
420
L (%)P1
0
0
0
0.003
0.008
0.012
0.015
0.022
0.024
0.024
0.032
0.041
0.048
0.051
0.064
0.071
L (%)P2
0
0
0.003
0.007
0.012
0.016
0.02
0.024
0.029
0.031
0.036
0.044
0.053
0.059
0.068
0.075
L (%)P3
0
0
0.002
0.004
0.01
0.014
0.018
0.023
0.027
0.031
0.036
0.044
0.051
0.058
0.067
0.073
L (%)P4
0
0.001
0.006
0.009
0.012
0.014
0.019
0.023
0.026
0.028
0.028
0.037
0.042
0.045
0.054
0.06
Results Contd: Expansion vs time 0.5
CEM II 100%
0.18
0.16
Expansion (%)
0.14
0.12
0.1
0.08
0.06
0.04
0.02
0
0
10
15
20
25
20
25
Time ^ 0.5(Days)
CEM II + 50% GGBS

0.035
0.03
Expansion (%)
0.025
0.02
0.015
0.01
0.005
0
0
10
15
Time ^ 0.5(Days)
CEM II + 70% GBS

0.04
0.035
Expansion (%)
0.03
0.025
0.02
0.015
0.01
0.005
0
0
10
12
14
16
18
20
Time ^ 0.5(Days)
CEM I 100%
0.4
0.35
Expansion (%)
0.3
0.25
0.2
0.15
0.1
0.05
0
0
10
15
Time ^ 0.5(Days)
20
25
CEM I + 70% GGBS

0.045
0.04
Expansion (%)
0.035
0.03
0.025
0.02
0.015
0.01
0.005
0
0
10
15
20
25
20
25
Time ^ 0.5(Days)
SRPC 100%
0.08
0.07
Expansion (%)
0.06
0.05
0.04
0.03
0.02
0.01
0
0
10
15
Time ^ 0.5(Days)
APPENDIX D: Concrete Permeability and Sorption Tests

Air permeability results
MA53
5.9
6.05
5.8
5.7
5.6
y = -0.054x + 6.2021
5.5
5.85
5.3
5.7
5
10
Time (mins)
15
20
MB15
Ln(Pressure)
5.8
5.7
5.6
y = -0.0473x + 6.1426
5.5
5.4
0
10
Time mins)
15
10
Time (mins)
15
20
15
20
15
20
y = -0.013x + 6.200
10
Time (mins)
MC16
6.15
5.9
6.1
Ln(Pressure)
5.8
5.7
5.6
5.5
MB16
6.16
6.14
6.12
6.1
6.08
6.06
6.04
6.02
6
5.98
20
MC15
y = -0.0283x + 6.1883
5.8
5.9
Ln(Pressure)
5.9
5.75
Ln(Pressure)
5.95
5.4
0
MA16
6.1
Ln(Pressure)
Ln(Pressure)
y = -0.0555x + 6.2162
6.05
6
y = -0.018x + 6.221
5.95
5.4
5.3
5.9
0
10
Time (mins)
15
20
10
Time (mins)
MD15
6.15
Ln(Pressure)
Ln(Pressure)
5.8
5.6
5.4
5.2
y = -0.0738x + 6.1296
6.1
6.05
4.8
5.95
0
10
Time (mins)
15
20
10
Ln(Pressure)
6.05
6
5.95
5.9
5.85
5.8
5.75 y = -0.0345x + 6.1994
5.7
5.65
15
y = -0.015x + 6.224
ME15
Ln(Pressure)
MD16
6.2
20
10
15
20
15
20
Time (mins)
SR15
SR16
6.2
6.19
Ln(Pressure)
5.6
Ln(Pressure)
15
y = -0.014x + 6.235
Time (mins)
5.8
10
Time (mins)
ME16
6.18
6.16
6.14
6.12
6.1
6.08
6.06
6.04
6.02
6
20
5.4
5.2
y = -0.082x + 6.1198
6.18
6.17
6.16
6.15
y = -0.006x + 6.223
6.14
4.8
6.13
0
10
Time (mins)
15
20
10
Time (mins)
Water permeability results
MA53
2.00E-07
MA16
7E-08
6E-08
1.00E-07
y = 3.87E-08x + 1.23E-08
5.00E-08
Water (m3)
Water (m3)
1.50E-07
5E-08
4E-08
3E-08
y = 1.78E-08x - 9.05E-09
2E-08
1E-08
0
0.00E+00
2
2.5
3
Time ^0.5
3.5
MB15
2.00E-07
2.5
3
Time ^0.5
3.5
MB16
7E-08
6E-08
1.00E-07
y = 2.35E-08x + 6.28E-08
5.00E-08
Water (m3)
Water (m3)
1.50E-07
5E-08
4E-08
3E-08
y = 1.30E-08x + 1.40E-08
2E-08
1E-08
0.00E+00
0
2
3
Time ^0.5
3.5
MC15
1.40E-07
1.20E-07
1.20E-07
1.00E-07
1.00E-07
8.00E-08
6.00E-08
4.00E-08
y = 3.12E-08x - 2.85E-09
0.00E+00
Time ^0.5
3.5
MC16
4.00E-08
0.00E+00
3
3.5
6.00E-08
2.00E-08
2.5
3
Time ^0.5
8.00E-08
2.00E-08
2
2.5
1.40E-07
Water (m3)
Water (m3)
2.5
y = 1.96E-08x + 3.96E-08
2.5
3
Time ^0.5
3.5
MD15
3.00E-07
1.20E-07
2.50E-07
1.00E-07
2.00E-07
1.50E-07
1.00E-07
y = 7.57E-08x + 1.96E-08
4.00E-08
0.00E+00
0.00E+00
2.5
3
Time ^0.5
3.5
ME15
y = 2.68E-08x + 1.26E-08
2.5
3
Time ^0.5
3.5
ME16
0.0000001
8E-08
1.00E-07
y = 4.07E-08x + 1.49E-08
5.00E-08
Water (m3)
1.50E-07
Water (m3)
6.00E-08
5.00E-08
2.00E-07
6E-08
4E-08
y = 2.15E-08x - 1.58E-09
2E-08
0
0.00E+00
2
2.5
3
Time ^0.5
3.5
2.5
3.5
Time ^0.5
SR15
3.00E-07
SR16
1.00E-07
2.50E-07
8.00E-08
2.00E-07
1.50E-07
y = 6.44E-08x + 2.96E-08
1.00E-07
Water (m3)
Water (m3)
8.00E-08
2.00E-08
MD16
1.40E-07
Water (m3)
Water (m3)
3.50E-07
6.00E-08
4.00E-08
y = 2.25E-08x + 5.29E-09
5.00E-08
2.00E-08
0.00E+00
0.00E+00
2
2.5
3
Time ^0.5
3.5
2.5
3
Time ^0.5
3.5
Water sorptivity
MA53
MA16
1.20E-07
5E-08
1.00E-07
4E-08
8.00E-08
Water (m3)
Water (m3)
6E-08
3E-08
2E-08
6.00E-08
4.00E-08
y = 2.27E-08x + 1.59E-08
y = 1.56E-08x - 6.25E-09
1E-08
2.00E-08
0.00E+00
2
2.5
3.5
2.5
Time ^0.5
Water (m3)
Water (m3)
2.5E-08
2E-08
1.5E-08
1E-08
y = 5.07E-09x + 6.55E-09
5E-09
0
2
2.5
3.5
y = 4.04E-09x + 1.76E-08
2.5
3.5
Time ^0.5
MC15
MC16
3E-08
1.00E-07
2.5E-08
8.00E-08
2E-08
Water (m3)
Water (m3)
MB16
4E-08
3.5E-08
3E-08
2.5E-08
2E-08
1.5E-08
1E-08
5E-09
0
Time ^0.5
1.20E-07
3.5
Time ^0.5
MB15
3E-08
6.00E-08
4.00E-08
1.5E-08
1E-08
y = 2.59E-08x - 4.23E-09
2.00E-08
5E-09
0.00E+00
0
2
2.5
3
Time ^0.5
3.5
y = 1.59E-08x - 3.35E-08
2.5
3
Time ^0.5
3.5
MD15
2.00E-07
4E-08
Water (m3)
1.50E-07
Water (m3)
MD16
5E-08
1.00E-07
y = 3.97E-08x + 2.36E-08
5.00E-08
3E-08
2E-08
y = 1.45E-08x - 1.21E-08
1E-08
0.00E+00
0
2
2.5
3.5
2.5
Time ^0.5
3.5
Time ^0.5
ME15
8E-08
ME16
1.2E-07
7E-08
1.0E-07
Water (m3)
Water (m3)
6E-08
5E-08
4E-08
3E-08
2E-08
8.0E-08
6.0E-08
4.0E-08
y = 2.66E-08x + 5.75E-09
y = 2.44E-08x - 2.35E-08
1E-08
2.0E-08
0.0E+00
2
2.5
3.5
2.5
Time ^0.5
6E-08
SR15
2.50E-07
3.5
SR16
5E-08
Water (m3)
2.00E-07
Water (m3)
3
Time ^0.5
1.50E-07
1.00E-07
y = 5.35E-08x + 2.76E-08
5.00E-08
4E-08
3E-08
2E-08
1E-08
0
0.00E+00
2
2.5
3
Time ^0.5
3.5
2.5
3
Time ^0.5
3.5
APPENDIX E: Sulfuric Acid Testing: Mass Loss Data (brushed)

MASS (g)
CUBE No.
5
15
16
6
7
8
9
10
11
12
13
14
Prism No.
1
2
3
4
MASS
(g/m2)
CUBE No.
5
15
16
6
7
8
9
10
11
12
13
14
PRISM No.
1
2
3
4
WEEK
0
2447
2434
2443
2436
2449
2448
2453
2456
2453
2487
2462
2473
1
2449
2437
2445
2438
2451
2451
2461
2464
2462
2511
2487
2500
2
2448
2436
2444
2438
2451
2451
2468
2473
2472
2517
2493
2502
3
2449
2435
2443
2439
2451
2451
2446
2449
2448
2498
2475
2486
4
2453
2435
2445
2439
2455
2452
2442
2446
2444
2497
2473
2485
12
2436
2446
3549
3535
3572
3596
3550
3527
3582
3611
3548
3526
3593
3623
3550
3528
3569
3588
3544
3528
3570
3582
16
MIX
20
MA
24
2446
2447
2446
2446
2453
2453
2454
2454
2454
2454
2357
2344
2238
2147
2071
1999
2406
2415
2318
2242
2170
2104
3550
3527
3395
3422
3551
3528
3227
3256
3551
3528
3101
3128
3550
3529
2996
3018
3552
3529
2891
2919
MIX
MA
WEEK
0
0
0
0
0
0
0
0
0
0
0
0
0
1
33
50
33
33
33
50
133
133
150
436
455
491
2
17
33
17
33
33
50
250
283
317
545
564
527
3
33
17
0
50
33
50
-117
-117
-83
200
236
236
4
100
17
33
50
100
67
-183
-167
-150
182
200
218
12
16
20
24
50
0
67
83
50
67
50
50
100
100
100
100
0
0
0
0
12
-93
116
174
-12
-104
243
313
12
-81
-35
-93
-58
-81
-23
-162
12
-93
-2052
-2017
-1650
-1817 -3583 -5100 -6367 -7567
-1018
-1055 -2818 -4200 -5509 -6709
23
-81
-4000
-3942
23
-81
-5461
-5426
12
-70
-6678
-6701
35
-70
-7896
-7849
MASS (g)
CUBE No.
3
4
5
6
7
8
9
10
11
12
13
14
PRISM No.
1
2
3
4
MASS
(g/m2)
CUBE No.
3
4
5
6
7
8
9
10
11
12
13
14
PRISM No.
1
2
3
4
WEEK
0
2423
2434
2421
2424
2423
2436
2445
2429
2442
2485
2485
2456
1
2426
2436
2422
2426
2426
2437
2441
2425
2440
2484
2485
2452
2
2426
2436
2422
2427
2424
2438
2438
2426
2434
2488
2487
2455
3
2426
2437
2423
2426
2425
2436
2422
2405
2417
2467
2472
2435
4
2424
2436
2422
2425
2425
2437
2411
2394
2406
2458
2463
2427
12
2422
2425
2425
2437
3485
3468
3494
3498
3486
3470
3483
3496
3487
3470
3488
3504
3484
3468
3466
3480
3485
3470
3448
3463
16
MIX
20
MB
24
2423
2423
2423
2424
2438
2438
2438
2438
2273
2281
2175
2099
2016
1956
2361
2325
2238
2161
2082
2019
3485
3470
3281
3303
3486
3470
3138
3156
3487
3470
3022
3044
3486
3471
2903
2931
3487
3473
2814
2845
MIX
MB
WEEK
0
0
0
0
0
0
0
0
0
0
0
0
0
1
50
33
17
33
50
17
-67
-67
-33
-18
0
-73
2
50
33
17
50
17
33
-117
-50
-133
55
36
-18
3
50
50
33
33
33
0
-383
-400
-417
-327
-236
-382
4
17
33
17
17
33
17
-567
-583
-600
-491
-400
-527
12
16
20
24
17
17
33
17
33
33
33
50
33
33
33
33
0
0
0
0
12
23
-128
-23
23
23
-70
70
-12
0
-325
-209
0
23
-533
-406
0
23
-2470
-2261
-2600
-2683 -4450 -5717 -7100 -8100
-2255
-2382 -3964 -5364 -6800 -7945
12
23
-4128
-3965
23
23
-5472
-5264
12
35
-6852
-6574
23
58
-7884
-7571
MASS (g)
CUBE No.
3
4
5
6
7
8
9
10
11
12
13
14
PRISM No.
1
2
3
4
MASS
(g/m2)
CUBE No.
3
4
5
6
7
8
9
10
11
12
13
14
PRISM No.
1
2
3
4
WEEK
0
2437
2434
2439
2421
2439
2438
2407
2435
2447
2478
2494
2472
1
2438
2437
2441
2424
2440
2440
2404
2433
2443
2478
2498
2475
2
2439
2436
2441
2425
2441
2440
2410
2439
2451
2485
2504
2481
3
2438
2436
2441
2423
2441
2439
2394
2427
2438
2471
2491
2470
4
2437
2435
2440
2423
2440
2439
2387
2420
2424
2461
2482
2457
3449
3472
3515
3475
3451
3477
3512
3476
3452
3476
3520
3486
3452
3475
3507
3471
3450
3476
3494
3452
3450
3475
3370
3334
12
MIX MC
20
24
16
2441 2442 2442 2440 2442

2424
2441
2439 2440 2440 2438 2441
2311
2311 2205 2122 2051 1986
2379
2353 2272 2198 2135 2078
3452
3476
3228
3193
3451
3475
3107
3064
3450
3475
2998
2957
3453
3478
2912
2868
MIX
MC
WEEK
0
0
0
0
0
0
0
0
0
0
0
0
0
1
17
50
33
50
17
33
-50
-33
-67
0
73
55
2
33
33
33
67
33
33
50
67
67
127
182
164
3
17
33
33
33
33
17
-217
-133
-150
-127
-55
-36
4
0
17
17
33
17
17
-333
-250
-383
-309
-218
-273
12
16
20
24
33
50
33
17
50
50
17
50
33
33
50
0
0
0
0
23
58
-35
12
35
46
58
128
35
35
-93
-46
12
46
-243
-267
12
35
-1681
-1635
-2067
-2267 -4033 -5417 -6600 -7683
-2091
-2164 -3636 -4982 -6127 -7164
35
46
-3328
-3270
23
35
-4730
-4765
12
35
-5994
-6006
46
70
-6991
-7038
MASS (g)
CUBE No.
3
4
5
6
7
8
9
10
11
12
13
14
PRISM No.
1
2
3
4
MASS
(g/m2)
CUBE No.
3
4
5
6
7
8
9
10
11
12
13
14
Prism No.
1
2
3
4
WEEK
0
2519
2516
2516
2527
2515
2500
2450
2446
2446
2502
2496
2481
1
2522
2518
2519
2529
2517
2504
2435
2433
2432
2496
2496
2480
2
2522
2518
2518
2529
2517
2502
2436
2434
2432
2497
2496
2481
3
2521
2518
2518
2529
2516
2503
2419
2419
2414
2482
2481
2468
4
2520
2517
2518
2528
2517
2502
2409
2411
2404
2475
2474
2457
3527
3499
3512
3503
3528
3504
3497
3484
3530
3505
3497
3489
3530
3503
3477
3461
3528
3502
3464
3444
3529
3503
3325
3297
WEEK
0
0
0
0
0
0
0
0
0
0
0
0
0
1
50
33
50
33
33
67
-250
-217
-233
-109
0
-18
2
50
33
33
33
33
33
-233
-200
-233
-91
0
0
3
33
33
33
33
17
50
-517
-450
-533
-364
-273
-236
4
17
17
33
17
33
33
-683
-583
-700
-491
-400
-436
0
0
0
0
12
58
-174
-220
35
70
-174
-162
35
46
-406
-487
12
35
-557
-684
12
16
MIX MD
20
24
2518 2519 2519 2519 2518

2529
2517
2503 2504 2503 2503 2502
2298
2297 2191 2104 2020 1957
2377
2364 2270 2199 2124 2063
3531
3503
3174
3136
3530
3504
3061
3024
3532
3504
2950
2916
3531
3504
2867
2838
MIX
MD
12
16
20
24
33
33
33
50
50
50
50
33
67
50
50
33
-2467
-2483 -4250 -5700 -7100 -8150
-2164
-2127 -3836 -5127 -6491 -7600
23
46
-2168
-2388
46
46
-3919
-4255
35
58
-5229
-5554
58
58
-6516
-6806
46
58
-7478
-7710
MASS (g)
CUBE No.
3
4
5
6
7
8
9
10
11
12
13
14
PRISM No.
1
2
3
4
MASS
(g/m2)
CUBE No.
3
4
5
6
7
8
9
10
11
12
13
14
PRISM No.
1
2
3
4
WEEK
0
2447
2437
2423
2427
2411
2446
2432
2420
2433
2471
2486
2470
1
2450
2437
2424
2427
2412
2449
2432
2422
2435
2483
2493
2480
2
2448
2440
2424
2427
2413
2448
2437
2425
2440
2486
2498
2484
3
2448
2438
2425
2428
2413
2448
2416
2407
2418
2460
2481
2464
4
2448
2438
2425
2427
2413
2448
2408
2396
2409
2458
2472
2455
3532
3471
3494
3469
3536
3476
3468
3489
3537
3476
3492
3478
3536
3475
3473
3451
3536
3473
3460
3440
3536
3474
3331
3329
12
16
MIX ME
20
24
2425 2426 2425 2425 2426

2428
2413
2448 2449 2448 2449 2449
2303
2313 2210 2127 2042 1982
2386
2372 2284 2215 2144 2080
3536
3475
3198
3199
3535
3475
3084
3076
3535
3476
2974
2952
3535
3476
2896
2870
MIX
ME
WEEK
0
0
0
0
0
0
0
0
0
0
0
0
0
1
50
0
17
0
17
50
0
33
33
218
127
182
2
17
50
17
0
33
33
83
83
117
273
218
255
3
17
17
33
17
33
33
-267
-217
-250
-200
-91
-109
4
17
17
33
0
33
33
-400
-400
-400
-236
-255
-273
12
16
20
24
33
17
33
33
50
33
33
50
50
33
50
50
0
0
0
0
46
58
-301
232
58
58
-23
104
46
46
-243
-209
46
23
-394
-336
46
35
-1890
-1623
-1950
-2000 -3717 -5100 -6517 -7517
-1818
-1782 -3382 -4636 -5927 -7091
46
46
-3432
-3130
35
46
-4754
-4557
35
58
-6029
-5994
35
58
-6933
-6945
MASS (g)
CUBE No.
3
4
5
6
7
8
9
10
11
12
13
14
PRISM No.
1
2
3
4
MASS
(g/m2)
CUBE No.
3
4
5
6
7
8
9
10
11
12
13
14
PRISM No.
1
2
3
4
WEEK
0
2481
2459
2470
2478
2482
2458
2461
2478
2464
2520
2509
2522
1
2482
2461
2471
2480
2483
2461
2451
2472
2452
2526
2514
2530
2
2482
2462
2472
2479
2483
2460
2448
2469
2450
2524
2512
2529
3
2482
2460
2471
2480
2483
2460
2431
2447
2434
2508
2498
2512
4
2482
2460
2471
2480
2483
2460
2423
2437
2425
2500
2490
2507
3543
3550
3542
3555
3546
3551
3541
3556
3546
3549
3537
3552
3546
3550
3512
3524
3545
3550
3504
3514
3545
3550
3395
3395
12
16
MIX SR
20
24
2461
2472 2472 2472 2472 2471
2484
2461 2462 2461 2462 2460
2337
2326 2190 2105 2028 1962
2415
2421 2309 2232 2159 2092
3546
3552
3211
3205
3546
3553
3075
3077
3547
3553
2965
2968
3548
3553
2875
2881
MIX
SR
WEEK
0
0
0
0
0
0
0
0
0
0
0
0
0
1
17
33
17
33
17
50
-167
-100
-200
109
91
145
2
17
50
33
17
17
33
-217
-150
-233
73
55
127
3
17
17
17
33
17
33
-500
-517
-500
-218
-200
-182
4
17
17
17
33
17
33
-633
-683
-650
-364
-345
-273
12
16
20
24
33
33
33
33
33
17
33
50
67
50
67
33
0
0
0
0
35
12
-12
12
35
-12
-58
-35
35
0
-348
-359
23
0
-441
-475
23
0
-1704
-1855
-2350
-2300 -4567 -5983 -7267 -8367
-1709
-1836 -3873 -5273 -6600 -7818
35
23
-3838
-4058
35
35
-5414
-5542
46
35
-6690
-6806
58
35
-7733
-7814
Mass Loss (g/m2)
Week
MA
MB
MC
MD
ME
SR
261
51
153
66
15
380
25
105
137
139
55
29
335
107
408
198
353
11
513
285
567
337
483
1601
2442
1984
2300
1844
1959
12
3586
4127
3567
4065
3415
4084
16
5047
5454
4974
5402
4762
5553
20
6314
6832
6182
6728
6117
6841
24
7505
7875
7219
7735
7121
7933
APPENDIX F: Sulfuric Acid Testing: Mass Loss Data (unbrushed)

MASS (g)
CUBE No.
17
18
MASS
(g/m2)
CUBE No.
17
18
WEEK
0
1
2
3
4
8
12
16
2468
2473 2480 2482 2478 2406 2304 2258
2472
2477 2486 2488 2487 2426 2318 2275
MASS (g)
CUBE No.
17
18
MIX
20
2219
2226
MIX
MA
WEEK
0
1 2
3
4
8
12
16
20
24
0
91 218 255 182 -1127 -2982 -3818 -4527 -5091
0
91 255 291 273 -836 -2800 -3582 -4473 -4927
WEEK
0
1
2
3
4
8
12
16
2469
2484 2498 2516 2512 2390 2294 2258
2494
2511 2526 2542 2548 2409 2310 2272
MIX
20
2220
2239
MASS
(g/m2)
CUBE No.
17
18
MIX
WEEK
0
1
2
3
4
8
12
16
20
0
273 527 855 782 -1436 -3182 -3836 -4527
0
309 582 873 982 -1545 -3345 -4036 -4636
MASS (g)
CUBE No.
17
18
WEEK
0
1
2
3
4
8
12
16
2459
2482 2496 2516 2529 2394 2299 2255
2484
2477 2517 2534 2549 2426 2329 2291
MASS
(g/m2)
CUBE No.
17
18
MA
24
2188
2201
MB
24
2213
2230
MB
24
-4655
-4800
MIX
20
2224
2262
MC
24
2231
2257
MIX
MC
WEEK
0
1
2
3
4
8
12
16
20
24
0
418 673 1036 1273 -1182 -2909 -3709 -4273 -4145
0
-127 600 909 1182 -1055 -2818 -3509 -4036 -4127
MASS (g)
CUBE No.
17
18
WEEK
0
1
2
3
4
8
12
16
2553
2563 2575 2580 2581 2471 2378 2331
2544
2557 2569 2580 2578 2453 2366 2325
MIX
20
2287
2286
MD
24
2266
2267
MASS
(g/m2)
CUBE No.
17
18
WEEK
0
1
2
3
4
8
12
16
20
24
0
182 400 491 509 -1491 -3182 -4036 -4836 -5218
0
236 455 655 618 -1655 -3236 -3982 -4691 -5036
MASS (g)
CUBE No.
17
18
WEEK
0
1
2
3
4
8
12
16
2478
2498 2512 2525 2534 2424 2326 2281
2483
2503 2513 2531 2541 2424 2338 2288
MASS
(g/m2)
CUBE No.
17
18
MIX
WEEK
0
1
2
3
4
8
12
16
20
0
364 618 855 1018 -982 -2764 -3582 -4000
0
364 545 873 1055 -1073 -2636 -3545 -4055
ME
MASS (g)
CUBE No.
17
18
WEEK
0
1
2
3
4
8
12
16
2510
2526 2540 2549 2540 2435 2337 2291
2529
2549 2556 2557 2552 2459 2351 2303
SR
24
2220
2229
MIX
MASS
(g/m2)
WEEK
CUBE No. 0
1
2
3
4
8
12
16
0
291 545 709 545 -1364 -3145 -3982
0
364 491 509 418 -1273 -3236 -4109
MIX
20
2258
2260
MIX
20
2245
2257
MIX
MD
ME
24
2262
2260
24
-3927
-4055
SR
20
24
-4818 -5273
-4945 -5455
Mass Loss (g/m2)
Week
MA
MB
MC
MD
ME
SR
61
194
97
140
243
219
158
370
425
286
389
346
183
577
649
377
577
407
153
589
820
383
692
323
982
1491
1118
1573
1027
1318
12
2891
3264
2864
3209
2700
3191
16
3700
3936
3609
4009
3564
4045
20
4500
4582
4155
4764
4027
4882
24
5009
4727
4136
5127
3991
5364
APPENDIX G: Sulfuric Acid Testing: Cube Strength Data
Days
Water
Acid
% Loss
0
28
56
168
57
57
58
60
57
50
35
21
0%
12%
40%
65%
Cube strength (MPa)
Compressive Strength: Mix MA
80
70
60
50
40
30
20
10
0
Cubes in water
Cubes in acid
Days
Water
Acid
% Loss
0
28
56
168
61
65
65
70
61
53
35
19
0%
18%
46%
74%
Cube strength (MPa)
Compressive Strength: Mix MB
28
56
84
Days
112
140
168
80
70
60
50
40
30
20
10
Cubes in water
Cubes in acid
0
0
Days
0
28
56
168
Water
58
58
63
65
Acid
58
51
37
22
% Loss
0%
12%
42%
66%
Cube strength (MPa)
Compressive Strength: Mix MC
28
56
84
Days
112
140
168
80
70
60
50
40
30
20
10
0
Cubes in water
Cubes in acid
28
56
84
Days
112
140
168
Days
0
28
56
168
Water
65
71
75
77
Acid
65
56
43
19
% Loss
0%
21%
42%
76%
Cube strength (MPa)
Compressive Strength: Mix MD
MD - 100% CEM I
80
70
60
50
40
30
20
10
0
Cubes in water
Cubes in acid
Days
0
28
56
168
Water
54
57
59
69
Acid
54
49
34
18
% Loss
0%
14%
42%
74%
Cube strength (MPa
Compressive Strength: Mix ME
28
56
84
Days
112
140
168
140
168
140
168
80
70
60
50
40
30
20
10
0
Cubes in water
Cubes in acid
28
56
84
112
Days
Days
0
28
56
168
Water
60
58
68
75
Acid
60
59
41
21
% Loss
0%
0%
40%
72%
Cube Strength (Mpa)
Compressive Strength: Mix SR
SR - 100% SRPC
80
70
60
50
40
30
20
10
0
Cubes in water
Cubes in acid
28
56
84
Days
112
APPENDIX H: Sulfuric Acid Testing: Expansion Data

MB1 WATER
Wk 0
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
MB3 ACID
Ref Bar
(mm)
6.62
6.717
5.79
5.852
6.454
6.46
6.147
6.151
6.052
6.059
6.242
6.249
6.599
6.608
Ref Bar
(mm)
Reading
(mm)
3.332
3.42
2.501
2.557
3.158
3.158
2.83
2.862
2.748
2.752
2.948
2.949
3.298
3.301
Reading
(mm)
L
(%)
MB2 WATER
Wk 0
0.003
0.001
0.000
-0.002
-0.008
0.003
-0.003
-0.004
0.001
-0.001
-0.002
-0.004
L
(%)
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
MB4 ACID
Wk 0
Wk 0
Wk 4
Wk 4
Wk 8
Wk 8
NO READINGS
Wk 12
Wk 12
Wk 16
Wk 16
Wk 20
Wk 20
Wk 24
Wk 24
Ref Bar
(mm)
6.634
6.732
5.814
5.869
6.46
6.46
6.146
6.153
6.055
6.059
6.246
6.251
6.606
6.61
Ref Bar
(mm)
6.689
6.779
5.85
5.88
6.46
6.461
6.151
6.081
6.058
6.06
6.249
6.252
6.608
Reading
(mm)
3.517
3.601
2.661
2.712
3.299
3.304
3.001
2.976
2.888
2.885
3.082
3.083
3.435
3.434
Reading
(mm)
3.48
3.558
2.687
2.668
3.226
2.862
2.823
2.807
2.798
2.989
2.992
3.344
L
(%)
-0.009
-0.010
-0.012
-0.010
-0.006
-0.018
-0.014
-0.017
-0.013
-0.015
-0.016
-0.018
L
(%)
0.023
0.004
-0.005
-0.008
-0.027
-0.015
-0.012
-0.016
-0.016
-0.016
-0.017
MB1 WATER
Wk 0
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
MB3 ACID
Wk 0
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
Ref Bar
(mm)
5.981
5.989
6.618
6.851
6.189
6.192
6.436
6.424
6.229
6.249
6.596
6.621
6.433
6.439
Ref Bar
(mm)
5.975
5.997
6.802
6.882
6.191
6.192
6.258
6.47
6.243
6.252
6.61
6.621
6.438
6.438
Reading
(mm)
2.621
2.625
3.345
3.476
2.807
2.823
3.138
3.047
2.887
2.861
3.213
3.23
3.046
3.047
Reading
(mm)
2.884
2.874
3.685
3.725
3.031
3.039
3.22
3.328
3.056
3.082
3.427
3.424
3.311
3.222
L
(%)
MB2 WATER
Wk 0
0.036
-0.004
-0.007
-0.002
0.026
-0.005
0.009
-0.010
-0.008
-0.011
-0.009
-0.011
L
(%)
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
MB4 ACID
Wk 0
0.002
-0.014
-0.015
-0.012
0.034
-0.008
-0.026
-0.019
-0.024
-0.030
-0.002
-0.037
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
6.608
Ref Bar
(mm)
5.956
5.994
6.664
6.869
6.19
6.192
6.234
6.448
6.232
6.251
6.605
6.62
6.437
6.439
Ref Bar
(mm)
5.985
6
6.848
6.883
6.192
6.192
6.396
6.484
6.245
6.254
6.624
6.618
6.438
6.431
3.347
Reading
(mm)
2.75
2.761
3.422
3.631
2.942
2.937
3.014
3.209
2.99
3.005
3.352
3.357
3.176
3.178
Reading
(mm)
2.851
2.822
3.625
3.665
2.981
2.976
3.188
3.246
3.013
3.019
3.354
3.372
3.177
3.171
-0.016
L
(%)
-0.004
-0.002
-0.006
-0.009
0.005
-0.002
-0.004
-0.005
-0.008
-0.012
-0.011
-0.011
L
(%)
-0.018
-0.016
-0.013
-0.015
-0.012
-0.024
-0.022
-0.023
-0.037
-0.027
-0.033
-0.033
MC1 WATER
Wk 0
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
MC3 ACID
Wk 0
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
Ref Bar
(mm)
6.135
6.132
6.034
6.038
6.214
6.244
6.05
6.058
6.25
6.248
6.612
6.62
6.434
6.434
Ref Bar
(mm)
6.133
6.133
6.035
6.039
6.233
6.247
6.058
6.056
6.251
6.253
6.614
6.619
6.437
6.438
Reading
(mm)
3.182
3.172
3.07
3.064
3.224
3.277
3.075
3.075
3.276
3.273
3.635
3.635
3.451
3.451
Reading
(mm)
2.949
2.951
2.833
2.83
3.07
3.037
2.829
2.831
3.015
3.016
3.385
3.379
3.196
3.194
L
(%)
MC2 WATER
Wk 0
-0.002
-0.006
-0.012
-0.003
-0.006
-0.009
-0.006
-0.006
-0.007
-0.010
-0.009
-0.009
L
(%)
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
MC4 ACID
Wk 0
-0.007
-0.010
0.008
-0.010
-0.018
-0.016
-0.021
-0.021
-0.018
-0.022
-0.023
-0.024
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
Ref Bar
(mm)
6.134
6.133
6.035
6.039
6.212
6.247
6.057
6.059
6.25
6.252
6.612
6.619
6.435
6.436
Ref Bar
(mm)
6.132
6.132
6.033
6.039
6.241
6.247
6.054
6.059
6.244
6.251
6.616
6.62
6.433
6.437
Reading
(mm)
3.085
3.076
2.885
2.893
3.157
3.142
2.895
2.833
3.027
3.045
3.386
3.381
3.203
3.202
Reading
(mm)
3.017
2.881
2.721
2.724
2.959
2.93
2.74
2.73
2.917
2.918
3.386
3.29
3.088
3.091
L
(%)
-0.037
-0.036
0.001
-0.019
-0.042
-0.068
-0.066
-0.060
-0.068
-0.072
-0.070
-0.071
L
(%)
-0.024
-0.026
-0.012
-0.026
-0.025
-0.031
-0.030
-0.033
0.008
-0.032
-0.038
-0.038
MD1 WATER
Wk 0
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
MD3 ACID
Wk 0
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
Ref Bar
(mm)
6.147
6.15
6.463
6.468
6.242
6.249
6.054
6.056
6.249
6.253
6.61
6.612
6.444
6.446
Ref Bar
(mm)
6.149
6.15
6.466
6.464
6.248
6.25
6.056
6.059
6.252
6.255
6.611
6.612
6.443
6.446
Reading
(mm)
3.134
3.1
3.374
3.396
3.141
3.145
2.951
2.953
3.145
3.148
3.502
3.495
3.32
3.323
Reading
(mm)
3.042
3.013
3.235
3.226
2.995
3.01
2.8
2.803
2.986
2.982
3.338
3.331
3.151
3.153
L
(%)
MD2 WATER
Wk 0
-0.016
-0.009
-0.020
-0.022
-0.021
-0.021
-0.022
-0.022
-0.023
-0.027
-0.030
-0.029
L
(%)
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
MD4 ACID
Wk 0
-0.038
-0.040
-0.046
-0.041
-0.048
-0.048
-0.052
-0.054
-0.054
-0.058
-0.062
-0.062
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
Ref Bar
(mm)
6.152
6.15
6.466
6.466
6.246
6.25
6.055
6.057
6.25
6.255
6.611
6.612
6.443
6.446
Ref Bar
(mm)
6.151
6.15
6.464
6.464
6.246
6.25
6.054
6.056
6.253
6.257
6.611
6.611
6.444
6.447
Reading
(mm)
2.98
2.966
3.298
3.274
3.219
3.108
2.98
2.884
3.114
3.07
3.432
3.427
2.253
3.254
Reading
(mm)
3.132
3.162
3.402
3.399
3.172
3.163
2.984
2.969
3.169
3.162
3.514
3.517
3.334
3.334
L
(%)
0.006
-0.003
0.063
0.017
0.044
0.004
0.019
0.000
0.002
0.000
-0.402
-0.003
L
(%)
-0.017
-0.018
-0.022
-0.027
-0.020
-0.027
-0.026
-0.030
-0.031
-0.030
-0.036
-0.038
ME1 WATER
Wk 0
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
ME3 ACID
Wk 0
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
Ref Bar
(mm)
5.962
5.819
6.464
6.444
6.148
6.153
6.049
6.053
6.253
6.254
6.614
6.616
6.44
6.443
Ref Bar
(mm)
5.964
5.716
6.467
6.46
6.153
6.153
6.052
6.054
6.253
6.254
6.615
6.616
6.443
6.443
Reading
(mm)
2.717
2.559
3.215
3.187
2.891
2.883
2.794
2.794
2.989
2.985
3.348
3.347
3.174
3.174
Reading
(mm)
2.662
2.574
3.209
3.259
2.988
2.981
2.882
2.87
3.075
3.062
3.405
3.402
3.222
3.213
L
(%)
ME2 WATER
Wk 0
0.004
0.001
0.001
-0.004
0.002
0.000
-0.002
-0.004
-0.002
-0.004
-0.002
-0.004
L
(%)
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
ME4 ACID
Wk 0
0.018
0.040
0.055
0.052
0.053
0.047
0.050
0.044
0.037
0.035
0.032
0.029
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
Ref Bar
(mm)
5.964
5.825
6.466
6.434
6.152
6.153
6.051
6.055
6.253
6.254
6.615
6.616
6.441
6.442
Ref Bar
(mm)
5.797
5.732
6.466
6.466
6.151
6.153
6.054
6.055
6.25
6.257
6.615
6.616
6.442
6.443
Reading
(mm)
2.876
2.732
3.372
3.337
3.047
3.043
2.995
2.959
3.148
3.147
3.508
3.506
3.332
3.33
Reading
(mm)
2.582
2.51
3.254
3.257
2.893
2.907
2.787
2.789
2.982
2.981
3.34
3.339
3.158
3.156
L
(%)
0.000
-0.002
-0.005
-0.007
0.015
-0.001
-0.005
-0.006
-0.006
-0.007
-0.006
-0.008
L
(%)
0.004
0.005
-0.014
-0.010
-0.018
-0.018
-0.018
-0.022
-0.021
-0.022
-0.025
-0.026
SR1 WATER
Wk 0
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
SR3 ACID
Wk 0
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
Ref Bar
(mm)
5.683
5.955
6.458
6.464
6.146
6.15
6.054
6.054
6.255
6.229
6.609
6.61
6.442
6.445
Ref Bar
(mm)
5.937
5.956
6.463
6.465
6.15
6.149
6.058
6.056
6.255
6.239
6.611
6.597
6.444
6.445
Reading
(mm)
2.672
2.889
3.224
3.185
2.869
2.853
2.748
2.743
2.942
2.905
3.297
3.297
3.123
3.119
Reading
(mm)
2.681
2.689
3.129
3.119
2.806
2.804
2.696
2.69
2.893
2.87
3.226
3.201
3.053
3.047
L
(%)
SR2 WATER
Wk 0
-0.067
-0.085
-0.084
-0.092
-0.096
-0.098
-0.099
-0.103
-0.098
-0.099
-0.101
-0.104
L
(%)
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
SR4 ACID
Wk 0
-0.027
-0.032
-0.031
-0.031
-0.038
-0.040
-0.038
-0.041
-0.047
-0.052
-0.050
-0.052
Wk 4
Wk 8
Wk 12
Wk 16
Wk 20
Wk 24
Ref Bar
(mm)
5.927
5.955
6.461
6.46
6.15
6.152
6.055
6.058
6.255
6.236
6.61
6.608
6.444
6.445
Ref Bar
(mm)
5.95
5.957
6.462
6.461
6.151
6.154
6.059
6.058
6.255
6.245
6.61
6.6
6.444
6.446
Reading
(mm)
2.592
2.631
3.131
3.083
2.817
2.758
2.711
2.678
2.875
2.841
3.222
3.213
3.045
3.044
Reading
(mm)
2.715
2.72
3.162
3.156
2.827
2.825
2.734
2.718
2.88
2.923
3.246
3.228
3.067
3.061
L
(%)
0.002
-0.017
0.001
-0.024
-0.004
-0.018
-0.018
-0.024
-0.021
-0.024
-0.026
-0.026
L
(%)
-0.025
-0.027
-0.035
-0.037
-0.035
-0.041
-0.055
-0.034
-0.051
-0.054
-0.056
-0.059

Ecocem Use of GGBS Concrete Mixes PDF

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UCD School of Architecture, Landscape

and Civil Engineering

Use of GGBS Concrete Mixes for

In sodium sulfate expansion tests, traditional CEM I cements performed significantly

Dr Ciaran McNally, Project Manager

LITERATURE REVIEW ......................................................................................................... 3

EXPERIMENTAL PROGRAMME: MATERIALS AND METHODS ................................. 4

Experimental Overview .................................................................................................... 4

Materials and methods ...................................................................................................... 5

Sodium sulfate expansion tests .................................................................................. 5

Sulfuric acid tests ....................................................................................................... 7

Ultrasonic Tests .............................................................................................................. 10

Review of current research ....................................................................................... 10

Experimental setup ................................................................................................... 11

Permeability tests ............................................................................................................ 13

Sodium sulfate expansion results ................................................................................... 14

Discussion of sodium sulfate expansion results ............................................................. 23

Dilution effect .......................................................................................................... 23

Permeability and porosity......................................................................................... 24

The Influence of C3A ............................................................................................... 25

Influence of C3S and C2S ......................................................................................... 27

Sulfate resisting capabilities of CEM II/A-L and GGBS concretes ......................... 27

Sulfuric acid test results .................................................................................................. 29

Mass loss results ....................................................................................................... 29

Discussion of deterioration mechanism ................................................................... 34

Cube strength tests ................................................................................................... 36

Sulfuric acid expansion tests .................................................................................... 37

Ultrasonic results ............................................................................................................ 38

Stiffness loss in due to sulfuric acid testing ............................................................. 38

Stiffness loss in concrete exposed to a 1% sulfuric acid solution ............................ 41

Discussion of ultrasonic results ................................................................................ 46

Microstructural Effects ............................................................................................. 46

Chemical effects ....................................................................................................... 48

Permeability, absorption and sorptivity results .............................................................. 49

Sulfate experimental programme.................................................................................... 51

Sulfuric acid programme ................................................................................................ 52

Ultrasonic analysis .......................................................................................................... 54

Sodium sulfate tests ........................................................................................................ 56

Sulfuric acid tests............................................................................................................ 57

vulnerable than others to aggressive chemical environments. Simply referring to these

Laboratory-based research methodologies, especially those incorporating the biological

3 EXPERIMENTAL PROGRAMME: MATERIALS AND METHODS

Sodium sulfate expansion tests

Sulfuric acid tests

Sulfuric Acid Tests

Sodium Sulfate Tests

Hanlons, Co. Kildare

CEM I, CEM II/A-L, SRPC

CEM I, CEM II/A-L, SRPC

(0%, 50% & 70%)

(0%, 50% & 70%)

10mm & 20mm

3.2 Materials and methods

Figure 3.1 Example of the ASTM C1012 standard mortar prisms

L = change of length at age x (%)

Figure 3.2 Comparator reader with reference bar

3.2.2 Sulfuric acid tests

Table 3.3 Concrete mix quantities for sulfuric acid tests

28 days curing water @20C

7, 14, 21 & 28 days

After 28 days curing water @20C

7, 14, 21, 28 days, then