Calcium Nitrate as a Multifunctional Concrete Admixture

by
Prof. Harald Justnes,
SINTEF Technology and Society, Concrete, Trondheim, Norway
Abstract
Industrial quality calcium nitrate can be utilized as concrete admixture in many ways.
Examples are given for applications as 1) Set accelerator, 2) Counteraction of retardation by
plasticizers while maintaining rheology, 3) Long term strength enhancer, 4) Anti-freeze
admixture or winter concreting admixture and 5) Inhibitor against chloride induced corrosion
of steel.
The first two points may achieved by small dosages (in the range 0.2-1% dry admixture
by mass of cement), point 3 and 4 at moderate dosages (1-3%), while the last point require
dosages in the higher end (3-4%).
Calcium nitrate as a set accelerator, and side effects of that, is well proven in practice over
many years, while the corrosion inhibitor effect was only discovered in the later years. Unlike
more well known inhibitors like calcium nitrite, calcium nitrate is harmless for the
environment and more cost-effective.
Key-words: Calcium Nitrate, Accelerator, winter concreting, corrosion inhibitor

INTRODUCTION
SINTEF has been working with calcium nitrate as concrete admixture since 1992 and
confirmed known applications (e.g. accelerator) as well as finding new ones (e.g. corrosion
inhibitor). Thus, the following chapters are divided into the main applications/properties; set
acceleration, counteraction of plasticizer retardation, long term strength improvement, winter
concreting admixture and corrosion inhibitor. However, due to limited number of pages, each
topic is only briefly discussed, but with emphasis on the main application set acceleration.
SET ACCELERATION
In the past, a concrete accelerator was synonymous with an admixture increasing the 1 day
compressive strength. It is only in the later years, with the implementation of the European
standards that the industry distinguishes between setting and hardening accelerators, realizing
practical utilizations of both admixture effects independently.
According to the European admixture standard EN 934-2 of 2001, a setting accelerator
must give at least 30 min initial setting time at 20C, and maximum 60% of the initial setting
time of the reference at 5C measured on mortar with equal flow. A hardening accelerator
should give minimum 120% compressive strength compared to the reference after 1 day at
20C, and minimum 130% compressive strength compared to the reference after 2 days at
5C, as measured on concrete of equal flow. Requirements are set to long term strength and
air also.
Note that the European standard uses the practical approach of equal flow of mixes
allowing variations in water-to-cement ratio (w/c). However, variations in w/c may mask the
chemical effects of admixtures, so more fundamental studies searching for active accelerators
tend to use constant w/c and cement content.
Concrete is a relative low priced construction material, which means that any high prices
chemical admixture must enhance its performance at a relative small dosage, or alternatively a

cheaper chemical can be allowed at moderate dosage. Hence, accelerators should be sought
among industrial bulk chemicals.
Calcium chloride, CaCl2, was an ideal accelerator being a combined setting and hardening
accelerator, in addition to being an industrial bulk product. However, in 1960s awareness on
corrosiveness of chlorides on embedded reinforcement arose and today chloride containing
admixtures is prohibited for steel reinforced concrete (limits are set to < 0.4% Cl- of cement
mass, or < 0.1% for structures serving in chloride containing environment).
In the search for a relatively cheap chloride-free accelerator, calcium nitrate, Ca(NO3)2,
has arisen as an alternative setting accelerator, but it must be combined with other
components to function as a hardening accelerator. Unless otherwise stated the calcium nitrate
(abbreviated CN) referred to here is of granulated, technical quality with formula
xNH4NO3yCa(NO3)2zH2O where x = 0.092, y = 0.500 and z = 0.826, or in other words
composed of 19.00 % Ca2+, 1.57 % NH4+, 64.68 % NO3- and 14.10 % H2O.
When testing accelerators, it is important to know that outcome may strongly depend on the
composition of the Portland cement used. Justnes and Nygaard [1] published the set accelerating
efficiency of calcium nitrate (CN) at 5-7C on pastes (w/c = 0.40) based on 5 different Portland
cements with a C3A content ranging from 7.4 to 1.0 %. The accelerating efficiency ranged from
very strong to slight and there was no correlation between set accelerating efficiency and C3A as
initially assumed, but rather surprisingly with the belite, C2S, content as plotted in Fig. 1. The
correlation between belite content and set accelerating efficiency of CN was confirmed by
Justnes and Nygaard [2] in a study of five other cement pastes at 5C.
Justnes and Nygaard [3] discussed the reason for acceleration efficiency differences among
Portland cements by analyses of the liquid of cement pastes prior to setting. They found a linear
correlation between the alkali content of the fluid of 9 cement pastes in the fresh state with the
reduction in initial setting time when 1.55 % calcium nitrate was added, as reproduced in Fig. 2.
In order to find out whether setting acceleration is dominated by the calcium cation or
nitrate anion in Ca(NO3)2, Justnes [4] tested the efficiency of both calcium nitrate (65% NO3due to some crystal water) and sodium nitrate (73 % NO3-) as set accelerators for 4 different
Portland cements pastes at 5 C by Vicat needle. The dosages were 0.00, 0.25, 0.50, 0.75 and
1.00 % calcium nitrate of cement mass, while sodium nitrate was dosed to give
correspondingly equimolar nitrate content. The influence on setting time is listed in Table 1.
From this limited study, calcium nitrate seems in general to be a substantially better set
accelerator than sodium nitrate for Portland cements. Specifically, Ca(NO3)2 gave shorter
setting time relative to reference than NaNO3 in 10 out of 12 comparative tests and about
twice or more reduction in setting time in 6 of the 12 cases. It seems like Ca2+ dominates
setting, while NO3- may have an effect as well, depending on cement type.
Temperature evolution profiles in insulated concrete (i.e. semi-adiabatic) and early
compressive strengths for concrete cubes cured at 20C have been measured for different
additions of Ca(NO3)2 [5]. The concrete composition corresponded to w/(c+s) = 0.45 and 4 %
silica fume replacement of cement for both CEMI 52,5R-LA and CEM I 42,5R. The accelerating
effect of Ca(NO3)2 was also compared to additions of calcium acetate, Ca(CH3COO)2, and
formate, Ca(HCOO)2, at equimolar concentrations of Ca2+ for 3.5 % Ca(NO3)2 added to the
CEM I 42,5R concrete. Calcium acetate and formate gave about the same acceleration according
to the temperature profiles in Fig. 3, while Ca(NO3)2 showed greater accelerating effect in spite
of soluble calcium ions dominating the set accelerating effect. The reason for the lesser
efficiency of calcium salts of organic acids (i.e. formate, acetate etc) may be due to partial
complex formation with one of the anions (e.g. CaOOCCH3+), meaning that the overall chemical
equilibrium of the paste fluid does not experience the same effective concentration of Ca2+ ions
as for Ca(NO3)2. The temperature profiles in Fig. 3 reveal that setting time is accelerated
(criterion is 2C above base line) and not the early strength development rate (i.e. temperature

increase slope not steeper than reference) which is of importance avoiding thermal cracks in
massive structures. Increased 8 h strength for HSC (CEMI 52,5R-LA) and OPC (CEM I 42,5R)
concretes with increasing CN dosage is due to increased maturity at this early age due to the set
acceleration.
Another important parameter to control when testing accelerators is the temperature.
Justnes et al [6] measured reductions in initial and final set at 5C, 13C and 23C for cement
pastes with 1.55% calcium nitrate and equimolar Ca dosage of calcium chloride hexahydrate,
and compared them with neat cement pastes (two different Portland cements). The results
revealed that the efficiency of calcium nitrate as set accelerator is higher at lower
temperatures.
COUNTERACTING RETARDATION BY PLASTICIZERS
Practical utilizations of set accelerators are often to start concrete hardening earlier to
avoid cooling of concrete in winter concreting or to counteract the retarding effect of
plasticizers. Rettvin and Masdal [7] showed that additions of 50 % technical calcium nitrate
solution (ammonium free) to concrete gave a set acceleration proportional with the dosage up to
0.50 % of the cement weight. They also described the utilization of calcium nitrate (0.25%
dosage) to secure the slip forming rate during the construction of the shafts for the Troll Gravity
Base Structure (369 m height) in the North Sea, since calcium nitrate (CN) counteracted the
retarding effect of the plasticizer sodium lignosulphonate used.
Justnes and Petersen [8, 9] showed that CN can partly counteract retardation of plasticizers
while maintaining rheology as exemplified by plastic viscosity and yield point according to the
Bingham model for mortars with different lignosulphonates and CN in Table 2. Calcium
chloride, CaCl2, and sodium thiocyanate, NaSCN, is also used for comparison. The 1 day
strength of these mortars given in Table 3 is an indication of the counteraction of retardation.
LONG TERM STRENGTH INCREASE
If pure calcium nitrate is used as set accelerator, very early strength (e.g. 8 h in Fig. 4) is
increased, but not 1 day strength. However, often the long term strength (from 28 days an
onwards) is increased in spite of equal porosity as illustrated after 220 days in Fig. 5 (same
mixes as in Fig. 4). Justnes [10] discussed potential reasons for long term strength increase.
WINTER CONCRETING ADMIXTURE
Calcium nitrate (CN) is approved as an anti-freeze admixture for winter concreting in Poland
with a typical dosage of 0.5-1% dry CN of cement mass. However, there is no standard test
for anti-freeze and the test often involves a period of freezing in the fresh state and thawing
before testing strength (i.e. does the concrete stand early freezing?). Thus, the effect may be a
result of set acceleration. The experiment described in Fig. 6 with temperature profiles of
concrete in insulated moulds placed in a cabinet at -10C for 1 day followed by another day at
+20C illustrates that earlier setting may result in slower cooling down, less minimum
temperature and a faster warming up. All this translates into 2 day strength of concrete with
1% CN of 20.60.3 MPa while the reference only reached 15.62.3 MPa (4 parallel cubes).
CORROSION INHIBITOR
Justnes [11] recently gave a short review of inhibitors against chloride induced corrosion
of steel reinforcement in concrete, and specifically compared the performance of calcium
nitrate with the more common inhibitor calcium nitrite. Among other evidence, a simple test
of casting rebars in the centre of concrete cylinders where chloride has been mixed into the
recipe has been made. The cylinders are stored at 38C and 90% RH with air access over the
years and inspected for cracks periodically as a result of expanding rust formation. When the

reference cracks, the cylinders with CN intermixed are also split open and the rebars taken out
for inspection. Fig. 7 shows such rebars after 3 years and that steel without CN present is
badly corroded, sample with 2% CN only have spots of surface rust and sample with 4% rust
have no sign of corrosion. It was concluded that calcium nitrate (CN) at least is equally
efficient as calcium nitrite as inhibitor, and that it in addition is cheaper and less harmful.
CONCLUSION
Calcium nitrate is a concrete admixture that can function as 1) Set accelerator, 2)
Counteraction of retardation by plasticizers while maintaining rheology, 3) Long term
strength enhancer, 4) Anti-freeze admixture or winter concreting admixture and 5) Inhibitor
against chloride induced corrosion of steel. Thus, it is fair to denote it a multifunctional
concrete admixture.
REFERENCES
1. Justnes, H. and Nygaard, E.C., "Technical Nitrate as Set Accelerator for Cement at Low
Temperatures", Cement and Concrete Research, Vol. 25, No. 8, 1995, pp. 1766-1774.
2. Justnes, H. and Nygaard, E.C., "Technical Nitrate as Set Accelerator for Cement at Low
Temperatures", Advances in Cement Research, Vol. 8, No. 30, Apr. 1996, pp.1-9
3. Justnes, H. and Nygaard, E.C.: "The Mechanism of Calcium Nitrate as Set Accelerator for
Cement", Proceedings of 10th International Congress on the Chemistry of Cement,
Gothenburg, Sweden, 2-6 June 1997, paper 3iii012, 8 pp.
4. Justnes, H.: Chloride-free Accelerators for Concrete Setting and Hardening, Proc. IV
Int. ACI/CANMET Conference on Quality of Concrete Structures and Recent Advances
in Concrete Materials and Testing, Recife, Brazil, 6-7 September 2005, 11pp.
5. Justnes, H. and Nygaard, E.C.: "Calcium Nitrate - A Multifunctional Concrete Admixture",
Proc. Int. Conf. on High-Performance Concrete, and Performance and Quality of Concrete
Structures", June 05-07 1996, Florianopolis, Brazil, pp. 514-525.
6. Justnes, H., Clemmens, F., Depuydt, P., Van Gemert, D. and Sellevold, E.J.: Setting
Accelerators for Portland Cement, Supplementary Paper of the Sixth International
Conference on Superplasticizers and Other Chemical Admixtures in Concrete, Nice,
France, 11-13 October 2000, CANMET/ACI SP-195, pp. 1- 16.
7. Rettvin, . and Masdal, T., "Use of Calcium Nitrate Solution as Set-Accelerating
Admixture in Slip forming of High Strength Concrete", Proc. ERMCO'95, Istanbul,
Turkey, 1995.
8. Justnes, H. and Petersen, B.G.: Counteracting Retardation of Cement Setting by Other
Admixtures with Calcium Nitrate, Proc. 5th CANMET/ACI Int. Symp. Advances in
Concrete Technology, July 29 August 1, 2001, Singapore, ACI SP 200-3, pp. 39-49.
9. Justnes, H. and Petersen, B.G.: Counteracting Plasticizer Retardation of Cement Setting
with Calcium Nitrate, Proc. Int. Conf. Innovations and Developments in Concrete
Materials and Construction, Dundee, Scotland, 9-11 September, 2002, p. 259-267
10. Justnes, H.: Explanation of Long-Term Compressive Strength of Concrete Cause by the
Set Accelerator Calcium Nitrate, Proceedings of the 11th International Congress on the
Chemistry of Cement (ICCC), 11-16 May, 2003, Durban, South Africa, pp. 475-484.
11. Justnes, H.: Corrosion Inhibitors for Concrete, Proceedings of the International
Symposium on Durability of Concrete I Memory of Prof. Dr. Raymundo, Rivera, 12-13
May, 2005, Monterrey, N.L. Mxico, pp. 179-199.

Table 1 Initial setting time for different cement pastes (w/c = 0.40) at 5C with different
dosages of calcium nitrate, Ca(NO3)2, and sodium nitrate, NaNO3. Setting times are
listed in hours with relative setting time (%) to reference in brackets.
CEMENT TYPE
Ca(NO3)2 (%)
0.00
0.25
0.50
0.75
1.00
NaNO3 (%)
0.25
0.50
1.00

CEM I 42,5R

CEM II A-V 42,5R

CEM I 52,5R-LA

8.10 (100)
5.50 (67.9)
5.25 (64.8)
5.33 (65.8)
4.30 (53.1)

6.75 (100)
5.41 (80.1)
4.41(65.3)
5.83 (86.4)
5.70 (84.4)

7.40 (100)
5.80 (78.4)
3.00 (40.5)
4.60 (62.2)
1.80 (24.3)

12.25 (100)
4.7 (38.4)
7.5 (61.2)
3.8 (31.0)
4.0 (32.7)

5.60 (69.1)
5.55 (68.5)
6.00 (74.1)

5.15 (76.3)
6.55 (97.0)
7.52 (111.4)

6.10 (82.4)
5.40 (73.0)
4.80 (64.9)

8.33 (68.0)
6.33 (51.7)
5.00 (40.8)

Table 2 Viscosity and yield point of 1:3 mortars (w/c = 0.5) with different combination of
admixtures 10 minutes after addition of water.
Mix after 10 minutes
0.3% Borresperse (BSP) Ca
0.3% BSP Ca / 0.5% CN
0.3% BSP Ca / 1% CN
0.3% BSP Ca / 1% CN / 0.2% NaSCN
0.3% BSP Ca / 1% CaCl2
0.3% Wafex P
0.3% Wafex P / 1% CN

Viscosity
p [Pas]
1.43
1.47
1.57
1.53
1.55
1.26
1.51

Yield point
0 [Pa]
56.5
58.8
67.2
53.1
65.0
49.5
52.2

Regression
factor, r2
0.9978
0.9949
0.9982
0.9968
0.9930
0.9976
0.9966

Table 3 Compressive strength (MPa) for 1:3 mortars (w/c = 0.5) with different admixture
combinations as a function of age.
Mix
Reference (0%)
0.3% Borresperse1 (BSP) Ca
0.3% BSP Ca / 0.5% CN
0.3% BSP Ca / 1% CN
0.3% BSP Ca / 1% CN / 0.2% NaSCN
0.3% BSP Ca / 1% CaCl2
0.3% Wafex P2
0.3% Wafex P / 1% CN
0.3% Wafex P / 1% CN / 0.2% NaSCN
0.3% Wafex P / 1% CaCl2
0.3% SNF3
1

1 day
18.40.6
5.80.1
10.30.2
13.20.3
15.40.3
151
0.50.3
8.30.2
13.20.2
10.30.3
18.60.8

3 days
342
311
341
332
351
391
301
281
341
371
361

7 days
442
462
461
431
471
492
441
402
442
461
441

28 days
542
592
652
592
663
613
591
583
584
584
563

Sugar reduced lignosulphonate, 2Lignosulfonate containing natural sugars,

3
Naphtalene sulphonate-formaldehyde condensate

Effect of belite content on CN accelerator efficiency

Initial set reduction (%)

75
65
55
45

y = 4,6022x - 41,923
35

R2 = 0,9133

25
15
14

16

18

20

22

24

26

Belite content (%)

Fig. 1 The linear correlation between accelerating efficiency of 1.55 % CN additions of

different cements and their belite content.

reduction in setting time (min)

450

y = -661,44x + 447,11
R2 = 0,8196

350

250

150

50
0,1

0,2

0,3

0,4

0,5

0,6

Na2O-equivalent (%) in w ater

Fig. 2 The reduction in setting time for Portland cement pastes when 1.55 % calcium nitrate is
added vs. the alkali content of the liquid phase 20 min after mixing.

Fig. 3 Temperature vs. hardening time curves for OPC concrete with equivalent dosages of
soluble calcium from nitrate, acetate and formate compared with reference concrete.

Compressive
strength (MPa)

8 h compressive strength

12
10
8
6
4
2
0

HSC
OPC

2
3
4
CN-dosage (%)

Fig. 4 Early compressive strength (8 h) for high strength Portland cement (HSC) and
ordinary Portland cement (OPC) concrete with different dosages of calcium nitrate
(CN).

Compressive strength
(MPa)

220 days compressive strength

100
95
90

HSC

85

OPC

80
75
0

CN-dosage (%)
Fig. 5 Compressive strength at 220 days for HSC and OPC concrete with different dosages
of calcium nitrate (CN).

Concrete in styrofoam molds at -10/+20 C

Ref Styrofoam

24

Cabinet

1% CN Styrofoam
Cabinet

Temperature (C)

18

12

1% CN
Ref

1% CN

Ref
0
0

16

24

32

40

48

-6

Cabinet
-12
Time (h)

Fig. 6 Temperature evolution in 100 mm cube moulds consisting of 20 mm Styrofoam walls

for insulation to simulate larger specimens (e.g. walls) placed in a -10C cabinet for 1
day followed by thawing at +20C for another day before testing of compressive
strength. Concrete with 1% calcium nitrate (CN) cooled down slower than concrete
without due to earlier setting, did not reach the low temperature and thawed faster. The
2 day strength of concrete with 1% CN was 20.60.3 MPa while the reference only
reached 15.62.3 MPa.

Fig. 7 Rebars removed from concrete cylinders with 3.2 % NaCl intermixed after 3 years
storage at 38C and 90% RH. Upper rebar from reference, middle rebar from concrete
with 2 % CN and lower rebar from concrete with 4% CN.