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Effects of Aggressive Ammonium Nitrate on Durability Properties of Concrete


using Sandstone and Granite Aggregates

Article · January 2013

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World Academy of Science, Engineering and Technology 73 2013

Effects of Aggressive Ammonium Nitrate on


Durability Properties of Concrete using
Sandstone and Granite Aggregates
L.L. Wong, H. Asrah, M.E. Rahman, and M.A. Mannan

and heavily damage it. Factors that affect the susceptibility of


Abstract—The storage of chemical fertilizers in concrete concrete to damage include chemical composition of its
building often leads to durability problems due to chemical attack. ingredients and physical factors such as porosity, density and
The damage of concrete is mostly caused by certain ammonium salts. permeability at the time of its exposure to corrosive agents.
The main purpose of the research is to investigate the durability
However, the maximum damage of concrete is reported to be
properties of concrete being exposed to ammonium nitrate solution.
In this investigation, experiments are conducted on concrete type G50 caused by ammonium salt.
and G60. The leaching process is achieved by the use of 20% Ammonium nitrate causes dissolution of cement-based
concentration solution of ammonium nitrate. The durability materials through the reaction between ammonium nitrate and
properties investigated are water absorption, volume of permeable calcium hydroxide in the cement paste. The reaction is
voids, and sorptivity. Compressive strength, pH value, and expressed in (1):
degradation depth are measured after a certain period of leaching. A
decrease in compressive strength and an increase in porosity are
found through the conducted experiments. Apart from that, the 2NH4NO3 + Ca(OH)2 Æ Ca(NO3)2 + 2NH3 + 2H2O (1)
experimental data shows that pH value decreases with increased
leaching time while the degradation depth of concrete increases with The reaction between ammonium nitrate and concrete was
leaching time. By comparing concrete type G50 and G60, concrete reported as potentially aggressive. Due to the removal of
type G60 is more resistant to ammonium nitrate attack. calcium hydroxide, the hardened cement paste will be
decalcified causing the pH value to decrease [2]. The reaction
Keywords—Normal weight concrete durability, Aggressive yields calcium nitrate and ammonia, both of which are easily
Ammonium Nitrate Solution, G50 & G60 concretes; Chemical attack. water-soluble. Subsequently, an expansive calcium nitro-
aluminate is formed by reaction between calcium nitrate and
I. INTRODUCTION hydrated aluminates from the cement paste [3]. Lea [4]

C ONCRETE is an economical construction material which


is employed in a wide variety of applications on the
ground, underground, and under sea level. It is used in
reported that this compound forms “climbing salts” by the
transportation of water from humid to dry surface. The
concrete is weakened through the leaching of lime in cement
foundations, pavements, storage tanks, piles, buildings, dams, paste. This eventually leads to cracking on the concrete
and other structures. Durability, compressive strength, surface. The deterioration of concrete reduces the
impermeability, abrasion resistance, and resistance to effectiveness of concrete as protective cover for steel
environment attacks are important properties of concrete. reinforcement. The steel reinforcement will be corroded,
Durability is the capacity of concrete to resist deterioration leading to spallation of concrete [2].
from heating and cooling, freezing and thawing, and action by The durability of concrete subjected to aggressive
chemicals such as fertilizers. Concrete that is durable requires environments is affected by transport properties, which are
the integration of design, materials, and construction. It influenced by the pore system [5]. Major factor influencing
depends on the materials used, full compaction, and adequate the durability is the permeability of the concrete. Permeability
curing [1]. Concrete exposed to aggressive environment lead allows the ingress of oxygen, carbon dioxide, water, and other
to deterioration of concrete. Chemical fertilizer plant is deleterious substances into the concrete. Permeability should
considered as aggressive environment. Different types of be kept to the minimum level by using sufficient cement
fertilizers will attack concrete contents, low water/cement (w/c) ratio, adequate compaction
and sufficient hydration of the cement through appropriate
curing methods [6].
L.L. Wong was with the Civil Engineering Program, School of
Engineering and IT, University Malaysia Sabah (e-mail: II. EXPERIMENTAL DETAILS
jenny_wil@hotmail.com).
H. Asrah is with the Civil Engineering Program, School of Engineering A. Materials for Concrete Mixtures
and IT, University Malaysia Sabah (e-mail: hidayati@ums.edu.my).
M.E. Rahman is in Department of Civil and Construction Engineering, Cement
Curtin University, Miri, Sarawak Malaysia (e-mail:
merahman@curtin.edu.my).
The cement used conforms to the requirements set under
M.A.Mannan was with the Civil Engineering Program, School of ASTM C-150 [7], Type 1 Ordinary Portland Cement.
Engineering & IT, University Malaysia Sabah. He is now with the Department
of Civil Engineering, University Malaysia Sarawak, Malaysia. (e-mail:
mannan@feng.unimas.my).

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World Academy of Science, Engineering and Technology 73 2013

Coarse Aggregate age) before testing. The container was closed by lid to prevent
Coarse aggregates composed of granite and crushed the ammonia gas produced by reaction of ammonium nitrate
sandstone within the range of 10 mm to 14 mm. Physical and calcium hydroxide to be evaporated in the air. To
properties of the coarse aggregates are given in the TABLE I. determine the durability properties, tests conducted were water
absorption, volume of permeable voids (VPV) and sorptivity
Fine Aggregates test. Other tests such as compressive strength test, pH
The size of river sand ranged from 75 μm to 4.75 mm. It measurement and degradation depth measurement were also
was dried in a shielded place for a week. Then, it was sieved determined.
to find the fineness modulus. Physical properties of the fine
aggregates are given in TABLE I. TABLE II
MIX PROPORTION OF CONCRETE TYPE G50 AND G60
Fly Ash
Concrete Type G50 G60
Fly ash used in this research to improve the workability and
ultimate strength of concrete. It also used to improve Cement (kg/m3) 500 440
resistance to sulphate attack and reduce permeability. Fly Ash (kg/m3) - 71.5
Silica Fume Silica Fume
30 38.5
(kg/m3)
Silica fume also added in concrete to produce high strength,
River Sand
dense and durable concrete. 500 312
(kg/m3)
Crushed
Superplasticizer - 220
Sandstone (kg/m3)
Superplasticizer was added to increase the strength of Granite (kg/m3) 1140 1056
concrete. It is a water-reducing admixture which facilitates
work with concrete of low w/c ratio. It is also used to Water (kg/m3) 186 165
eliminate segregation of concrete and allow good dispersion of S.P (%) 1.67 1.67
cement particles in water, accelerating the rate of hydration
[8].
III. TEST RESULTS AND DISCUSSIONS
TABLE I
PROPERTIES OF COARSE AND FINE AGGREGATES A. Compressive Strength Test
Characteristics Granite
Crushed
River Sand
The testing procedure is complied with BS 1881: Part 116:
Sandstone 1983 [9]. The results for the compressive strength test are
10mm to 75μm to
Size Range
14mm
10mm
4.75mm
shown in Fig. 1. The compressive strength decreased when the
Fineness concrete was treated with ammonium nitrate solution. For
- - 2.18
Modulus concrete type G50, the strength decreased to 42.71 N/mm2 at
Moisture Content 0% 1.27% 0% the age of 56 days whereby there was a difference of 24.91%
in strength compared to the concrete cured in water at the
Specific Gravity 2.80 2.62 2.74 same age. It continued to decrease until 30.88 N/mm2 at the
age of 90 days, leading to a difference of 47.44% compared to
B. Concrete Sample Preparations
those immersed in water. For concrete type G60 treated with
The mix proportions were prepared as in TABLE II. The ammonium nitrate solution, the strength decreased from 51.11
mixer was pre-damped with water. Half of the coarse N/mm2 at the age of 56 days to 38.28 N/mm2 at the age of 90
aggregate was added and then followed by fine aggregate and days. The percentage of difference in strength between
finally the remaining coarse aggregate by spreading them concrete treated with ammonium nitrate solution and water at
evenly over the pan and the mixer was operated for 30 second. the age of 56 days was about 22.48% while for concrete at the
After that, half of the water is mixed for 1 minute. The age of 90 days, the difference in strength was 42.06%. The
cement, silica fume and fly ash were added in an even layer loss of strength for concrete type G60 was less than concrete
over the aggregate. The mixture was then mixed for 1 minute. type G50 after leaching by ammonium nitrate solution,
Finally, the remaining water and superplasticizer were added indicating that concrete type G50 was more susceptible to
and mixed uniformly to produce concrete grade 50 and 60. damages done by ammonium nitrate solution compared to
The concrete was then placed in the cube mould in three layers concrete type G60.
and each layer was compacted by using vibrating table. The Based on the research of Carde and Francois [10], the loss
concrete specimens were left undisturbed for 24 hours and of strength was essentially due to the removal of calcium
then demoulded. The specimens were cured for 3, 7, 28, 56, hydroxide during the leaching process by ammonium nitrate
and 90 days respectively in the water tank for normal curing solution. Calcium hydroxide is the hydration product which
method. replaces the space occupied by cement and water during
After 28 days curing of specimens, some of the specimens hydration process. The calcium hydroxide reacts with
were partially immersed in ammonium nitrate solution with ammonium nitrate yielding calcium nitrate and ammonia
concentration of 20% until 56 day and 90 day (include curing

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World Academy of Science, Engineering and Technology 73 2013

which are easily dissolvedd in water. Removal


w R of calcium
c disssolution of caalcium hydroxxide caused by y ammonium nitrate
hyydroxide prodduces voids orr pores within n the concretee. These sollution. Remooval of calciium hydroxid de introducess more
vooids weaken thhe strength off concrete [8]. vooids within cooncrete and inncreases the porosity
p of cooncrete.
Ass porosity inccreases, the diiffusion coeffficient of calccium is
alsso increased leading to higher rate of hydrates being
disssolved. This results in the modification of microstruccture of
thee concrete, causing
c an iincrease in permeability
p and a
decrease in bulkk density [13]..
C. Volume off Permeable V
Voids (VPV)
The procedurres of VPV tesst are complieed with ASTM M C642
[11]. The resultts for volume of permeablee voids are shoown in
Figg. 3. VPV valuue for concrette type G50 an nd G60 decreaased as
thee curing age in water inccreased. The ammonium nitrate
sollution causedd the permeeable of con ncrete to inncrease,
theerefore, seriouusly affectingg the durabiliity of the cooncrete.
Thhe difference of VPV value of concretee immersed in n water
Fig. 1 Compreessive strength of concrete imm
mersed in water and annd ammonium m nitrate solutiion at 56 dayys was about 1.12%
ammoonium nitrate solution with diffferent ages forr concrete typpe G50. The difference inccreased to 2.333% at
B. Water Abssorption 900 days immerssion. The incrrease in water absorption wasw due
to removal of calcium hydrroxide within concrete porre. For
Water absorrption identifiies the capabbility of conccrete to
concrete type G60,
G the VPV V value of cooncrete treateed with
abbsorb water. The
T procedurees are complieed with ASTM M C642
ammmonium nitrrate increasedd with immerssion time, hoowever,
[111]. The resultts for the water absorption are shown inn Fig. 2.
thee increase in VPV
V was lower than that off concrete typpe G50.
Thhe water absorption decreeased with cooncrete age for fo both
It differs abouut 0.87% at 56 days com mpared with those
cooncrete type G50
G and G60 ccured in waterr. After immerrsion in
mmersed in waater. The VPV
im V value record ded at the agee of 90
ammmonium nittrate solutionn, concrete type t G50 annd G60
daays shows an inncrement of 22.13%.
abbsorbed more water than thhose cured in water.
w The inncreased
The VPV valuev of botth concrete increased
i wiith the
abbsorption ratee with leachinng time was similar with results
im
mmersion periiod. The valuues were also o higher thann those
reeported by Aggostini et al. [12]. The caapability of concrete
c
im
mmersed in waater. It may bbe due to disssolution of calcium
tyype G50 to abbsorb water waas higher thann concrete typpe G60.
hyydroxide in cooncrete pore. T The reductionn in concentraation of
Thhe differencee between thhe water absorption of concrete
c
ionns in the porre solution foorced the disssolution of calcium
c
treeated in ammoonium nitrate solution and water at 56 daays was
hyydroxide. Thiss resulted in increased off material poorosity,
0.75% for conccrete type G550. The difference kept inccreasing
permeability andd reduced meechanical propperties [14]. Calcium
C
too 1.92% at 900 days. For concrete
c type G60, the diffference
hyydroxide acts as hydration product whiich fills in thhe pore
w lower thann that of concrrete G50. It recorded
was r a diffference
sysstem within thet concrete. Removal off calcium hyddroxide
off 0.69% comppared to thosee immersed inn water at thee age of
froom the pore increases thee voids causiing the concrrete to
566 days. At 90 days, it was 11.27% higher than those immmersed
become more peermeable.
inn water.

Fig. 2 Wateer absorption off concrete immeersed in water and


a
ammoonium nitrate solution with diffferent ages F 3 VPV valuues of concrete immersed in water
Fig. w and ammoonium
nitrate solutionn with different ages
The averagee water absorrption of conncrete type G50 G and
G60 was higherr than those cuured in water.. It may be duue to the
G

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World Academy of Science, Engineering and Technology 73 2013

D. Sorptivityy reccorded to be 11.40%. Thhen, the diffeerence of pH H value


Sorptivity test measures capillary
c suction of concrette when droopped when testing deppth increased d. The pH value
it is in contact with water. Itt is an index ofo moisture trransport decreased from m 4.75% to 0..50% for the depth of 5-1 10 mm
in
nto unsaturated specimens; therefore it had h been reco ognised unntil 20-25 mm. For concretee age of 90 daays, the result shows
ass an importaant index off concrete durability
d [15
5]. The a ddecrease of pHH value from 113.70% to 0.9 98%.
prrocedures used are as described by Chaan and Ji [16]. Fig. 4 The pH valu ue for concrette type G60 alsoa decreaseed with
shhows the resullts of sorptivity of concretee type G50 an nd G60. im
mmersion perio od. It recordedd pH 11.30 att the age of 56
5 days
Th he sorptivity coefficients
c off concrete treaated with ammmonium an
nd pH 11.13 at a the age of 990 days for th he depth of 0--5 mm.
niitrate solution
n increased with
w the time of o immersion n. There Thhe reduction was
w about 7.53 3% and 9.00%% at 56 days and 90
w a differencce of about 27
was 7.4% in sorptiivity at the agge of 56 daays concrete age,
a comparedd with those immersed in water.
daays for concrete type G550 treated in n ammonium nitrate Thhe reduction ofo pH value bbecame smalleer when testin ng was
coompared with h those immerrsed in water at the same age. At conducted for further
f depth. It shows a decreasing
d of 0.33%
th
he age of 90 days, the diifference in sorptivity
s coeefficient nd 0.57% in pH
an p value for tthe testing dep pth of 20-25 mm at
in
ncreased to ass much as 344.8%. For con ncrete type G60,
G the thee age of 56 daays and 90 dayys.
diifference wass only 9.3% % for ammon nium nitrate treated Decreasing in pH values when immeersed in amm monium
cooncrete at the age of 56 dayys compared to t those immeersed in nittrate solution
n may due to o the dissoluttion of hydraates in
w
water at the same age. Subssequently, thee sorptivity increased concrete. Kamaali et al. [19] indicate that the
t lower the pH of
222.0% at 90 day ys of age. thee aggressive water
w and highher the concen
ntration gradieent, the
The increasiing of sorptivvity coefficient is caused by the difffusion of hydroxyl
h ionns would bee significantt. The
m
modification of pore structuure. Ammoniium nitrate reemoves am
mmonium nitrate solution leed to a pure dissolving
d corrrosion
caalcium hydroxide from th he concrete pore.
p This prroduces byy a neutralizatiion reaction. TThis showed that the pH value in
m
more voids witthin the concrrete, thus incrreasing the ab bility to thee attacked part
p of the sspecimens waas reduced by b the
abbsorb more water.
w Accordiing to Haga et al. [17], th he pore neutralization reeaction [2].
voolume becamee larger with leaching
l perioods. The increeased of
TA
ABLE III
poore volume became
b largerr with a larg ger decreased in the RESULTS OF
O PH VALUE OF CONCRETE AT DIFFERENT AGES
quuantity of calccium hydroxid de. The increased in pore volume
Age (D
Days)
w
were attributable to the dissoolution of calccium hydroxid de. The
raate of water abbsorption by concrete typee G60 is slow wer than 56 90
th
hat of concreete type G50 0. It may bee due to thee lower C
Concrete Deepth Water NH4NO3 Water NH4NO3
diissolution of calcium hy ydroxide in concrete typ pe G60 mm)
(m
T
Type
coompared to thaat of concrete type G50.
0--5 12.20 10.81 12.20 10.553
5--10 12.23 11.65 12.23 11.334
G
G50 100-15 12.24 11.91 12.25 11.774
155-20 12.26 12.02 12.26 11.889
200-25 12.27 12.21 12.27 12.115
0--5 12.22 11.30 12.23 11.113
5--10 12.25 12.09 12.25 12.003
G
G60 100-15 12.27 12.17 12.27 12.113
155-20 12.27 12.24 12.28 12.222
200-25 12.29 12.25 12.30 12.223

F. Degradatioon Depth Meaasurement


Fig. 4 Sorptiv
vity of concrete immersed in water
w and ammonium The degradattion depth is ddefined as the distance fromm inner
n with differentt ages
nitrate solution fro
ont to the exteernal surface of the materiial. It increasees with
E. pH Measu
urement thee dissolution of
o hydrates [19]. The procedures are refeerred to
The procedu ure is referreed to Geotecchnical Engineering Ngguyen et al. [20].
[ Fig. 5 sshows the ressults of degraadation
Bu ureau [18]. The
T results of pH values fo or concrete typpe G50 deppth for both concrete
c type G50 and G60 0. It can be ob
bserved
annd G60 immeersed in wateer at specified age are sh hown in thaat the degradaation depth inccreased with immersion tim me. The
TA ABLE III. Fo or concrete ty
ype G50, the pH value decreased slo
ope of the graaph for concreete type G60 was less steeep than
affter immersed d in ammoniu um nitrate soolution for 56
6 days. thaat of concrette type G50. It shows a smaller vaalue of
In
nitially, the pH
H value is 10.81 for the dep
pth between 0-5
0 mm coefficient k with
w 0.67 coompared with h coefficient k for
att the age of 565 days. The difference in n pH value between
b concrete G50 which
w was 0.777.
cooncrete immeersed in amm monium nitraate and water was

1110
World Academy of Science, Engineering and Technology 73 2013

[4] Lea, F.M. 196 65. The action of aammonium salts on concrete. Maggazine of
Concrete Reseearch 17(52): 1155-116.
[5] Maltais, Y., Samson, E. & Maarchand, J. 2004. Predicting the durability
d
of Portland Cement
C systems in aggressive environments:
e laaboratory
validation. Cemment and Concreete Research 34(9 9): 1579–1589.
[6] Barr, B.I.G. 2003. Failure of concrete sttructures. Cardiiff, UK:
University of Wales.
W
[7] ASTM C150 0/C150M – 11 “Standard Speecification for Portland
Cement.”
[8] Shan Somayajji. 2001. Civil Enggineering Materiials-Second Editiion. New
Jersey: Prenticce Hall.
[9] BS 1881: Part P 116:1983. 1983. Method for Determinaation of
Compressive Strength of Conncrete Cubes. Lo ondon: British Standards
S
Institution.
0]
[10 Carde, C. & Francois,
F R. 19997 (a). Aging daamage model of concrete
Fig. 5 Graph
h of degradationn depth versus square
s root of tiime behavior durring the leachin ng process. Materials
Ma and sttructures
constructions 30: 465-472.
According to t Nguyen eet al. [20], the leaching g depth [11
1] ASTM C642. 2002. Standard T Test Method for Density, Absorpttion, and
Voids in Hard dened Concrete. Annual Book off ASTM Standardds 2002,
in
ncreased with h leaching du uration. Schneeider and Ch hen [2] 04.02. Philadeelphia: American Society for Testiing and Materials.
fo
ound out that the degradatiion depth dep pended on thee initial [12
2] Agostini, F., Lafhaj, Z., Skkoczylas, F. & Loodsveldt, H. H 2007.
strrength of the specimens. Concrete
C with
h higher strenggth had Experimental study of acceleerated leaching on hollow cylin nders of
mortar. Cemennt and Concrete R Research 37: 71-7 78.
lo
ower value of coefficient k. Based on n this researrch, the [13
3] Yang, H., Jiaang L., Zhang Y Y., Pu, Q., Xu, Y. 2012. Prediccting the
co
ompressive strrength at the age of 28 daays for concreete type calcium leachiing behavior of ccement pastes in aggressive
a enviroonments.
2
G is 52.67 N/mm
G50 N while concrete
c type G60 recorded d 62.01 a Building Matterials 29: 88-96..
Construction and
N
N/mm 2
. The deegradation dep
pth of concrette type G60 is 0.067 [14
4] Jain, J., & Neiithalath, N. 2009.. Analysis of calccium leaching beh havior of
plain and mod dified cement paastes in pure waater. Cement & Concrete
C
X square root ofo time while concrete typee G50 recorded d 0.077 Composites 31 1: 176-185.
X square root of time. It shhows that con ncrete type G60
G had [15
5] Dias, W.P.S. 1995. Sorptivity Testing for Assessing Concrete Quality.
lo
ower value off coefficient k than concrrete type G50. This Proc. Int. Conf.
C on Concreete under Severre Exposure Coonditions
(CONSEC '95). Spon, London.. Pp. 433-442.
in
ndicates that concrete typee G50 was more m suscepttible to [16
6] Chan, SYN. anda Ji X. 1998. W Water sorptivity an nd chloride diffu
usivity of
deegradation cau used by amm monium nitratee solution compared oil shale ash concrete. Construcct Build Mater 12 2(4): 177-183.
to
o concrete typee G60. [17
7] Haga, K., Suttou, S., Hironagaa, M., Tanaka, S. S & Nagasaki, S. 2005.
Effect of poro osity on leachingg of Ca from harrdened ordinary portland
cement paste. Cement and Concrete Research 35: 1764-1775.
IV. CONCLUSION [18
8] Geotechnical Engineering B Bureau. 2007. Test Method for the
determination of pH value of w water or soil by pH H meter. New Yo ork State
Based on the experim mental resullts, the folllowing Department off Transportation.
co
onclusions weere made: [19
9] Kamali, S., Gerard, B. & Morranville, M. 2003 3. Modelling the leaching
1)) Concrete type
t G60 perfforms better annd is less suscceptible kinetics of cement-based m materials: Influeence of materials and
environment. Cement
C and Conccrete Compositess 25: 451-458.
to damage compared to concrete typee G50 when leached l [20
0] Nguyen, V. H.,H Colina, H., T Torrenti, J.M., Boulay,
B C. & Needjar, B.
by ammoniium nitrate soolution. 2007. Chemo mechanical couppling behavior off leached concrette part I:
2)) The loss off strength of cconcrete type G60 is less thhan that Experimental results.
r Nuclear EEngineering and Design 237: 2083-2089.
of concretee type G50 aftter immersed ini ammonium m nitrate
solution for a certain perriod.
3)) After the leaching proccess, the durability properrties of
concrete tyype G60 was higher than thatt of concreete type
G50.
4)) The pH measurement
m shows that the
t reduction in pH
values forr concrete ty ype G60 is lower than that of
concrete type
t G50 w when they were subjeccted to
immersion in ammoniuum nitrate so olution for different
d
immersion time.
5)) The rate of degraded deepth for concrrete type G60 0 is less
than that off concrete typpe G50.

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