Вы находитесь на странице: 1из 16

CEMENT and CONCRETE RESEARCH. Vol. I I , pp. 307-322, 1981. Printed in the USA 0008-8846/81/030307-16502.

00/0 Copyright (c) 1981 Pergamon Press, Ltd.

SUPERSULPHATED CEMENT FROMBLASTFURNACE SLAG AND CHEMICAL GYPSUM AVAILABLE IN THE NETHERLANDS AND NEIGHBOURING COUNTRIES

J. Bijen, E. NI~I Intron I n s t i t u t e , Maastricht, The Netherlands

(Communicated by A.J. Majumdar) (Received Dec. 15, 1980)


ABSTRACT The present report covers research i n t o the mechanical s t r e n g t h development and the surface hardness o f supersulphated cement from b ] a s t f u r n a c e s l a g , chemical gypsum and p o r t l a n d c l i n k e r . The t e s t s were c a r r i e d out on sand/cement mortar as well as on concrete. A co~lparison was.made w i t h a type of supersulphated cement which was in the market u n t i l r e c e n t l y , and w i t h p o r t l a n d and b l a s t f u r n a c e cement. A review has been made of the e f f e c t s of the hardening temperature, the r e l a t i v e h u m i d i t y , the degree o f g r i n d i n g of the cement, the use o f a w a t e r - r e d u c i n g a d d i t i v e , and treatment w i t h a curing compound. The conclusion is drawn that one o f the cements produced, c o n s i s t i n g of 83~ m/m Dutch b l a s t f u r n a c e slag, 15~ m/m fluorogypsum ( a n h y d r i t e ) and 2~ m/m p o r t l a n d c l i n k e r ground to the r e l a t i v e l y high s p e c i f i c surface o f 500 m2/kg, is not i n f e r i o r to b l a s t f u r n a c e cement as regards the p r o p e r t i e s examined. Yon S u l f a t h 0 t t e n z e m e n t , he r g e s t e l l t aus Hochofenschlacke und Chemiegips und P o r t l a n d z e m e n t k l i n k e r i s t die mechanische St~rkeentwicklung und die Oberfl~chenh~rte untersucht worden. Die Untersuchung i s t sowohl mit Sand/Zement- wie auch mit Betonn~rtel durchgefOhrt worden. Es i s t e i n V e r g l e i c h mit einem bis vor kurzem auf dem Markt e r h ~ l t l i c h e n Sulfath0ttenzement und mit Portland und Hochofenzement gemacht worden. Der E i n f l u s s yon Erh~rtungstemperatur, r e l a t i v e r F e u c h t i g k e i t , M a h l f e i n h e i t des Zements, der Anwendung eines wasserreduzierenden Z u s a t z m i t t e l s und der Nachbehandlung mit einem C u r i n g m l t t e l auf diesen Eigenschaften ] s t nachgegangen. Schlussfolgerung i s t , das e i n e r der h e r g e s t e l l t e n Zernent zusammeng e s t e l l t aus 83 Gew. ~ n i e d e r l ~ n d i s c h e r Hochofenschlacke, 15 Gew.~ Fluorogips ( A n h y d r i t ) und 2 Gew.~ P o r t l a n d k l i n k e r und bls zur r e l a t i v hohen s p e z i f i s c h e n Oberfl~che von 500 m2/kg gemahlt was den untersuchten Eigenschaften angeht einem Hochofenzement n i c h t nachzustehen braucht. 307

308 J. B i j e n , E. Ni~l

Vol.

II,

No. 3

INTRODUCTION The Dutch Ministry of Public Health and Environmental Protection, in the context or recommendations to be formulated on the subject of 'ffhe use of alternative materials and/or processes for production of cement, clinker or limestone, issued a commission for a preliminary study into the potential applications of supersulphated cement on the basis of blastfurnace slag and chemical gypsum available in the Netherlands or from neighbouring countries.

Portland c l i n k e r has a high calcium content (about 63% CaO), i t s main components being t r i c a l c i u m s i l i c a t e , C3S , and dicalcium s i l i c a t e , C^S. These Calcium s i l i c a t e s are p r a c t i c a l l y the only e x i s t i n g c r y s t a l l i n e z calcium s i l i c a t e s which react s u f f i c i e n t l y r e a d i l y with water. The reaction products, CSH(I) and CSH (11) Which provide most of the mechanical s t r e n g t h of the cement rock thus formed, contain much less calcium, however. The remaining calcium is mainly present as calcium h y d r o x i d e , f o r the g r e a t e r part c r y s t a l l i n e , and does not c o n t r i b u t e to the mechanical s t r e n g t h . Moreover, in p r a c t i c e a s u b s t a n t i a l p r o p o r t i o n (20 to 50%) of the cement remains unhydrated owing to the l i m i t e d rate of d i f f u s i o n of the reacting components. Of the calcium e v e n t u a l l y present in the cementstone, approximately 50 to 70% is not f u n c t i o n a l as regards mechanical s t r e n g t h . Calcium s i l i c a t e s w i t h less calcium do not react w i t h water in t h e i r c r y s t a l l i n e form. In the form of glass, however, they are r e a c t i v e i f a c t i v a t e d by a h i g h l y a l k a l i n e medium.
An example of such a glass substance is granulated blastfurnace slag, consisting to 95% of glass and containing about 30-55% m/m CaO and 25-50% m/m SiO 2 In view of the prospect of a possible shortage of primary calcium (limestone) in the Netherlands it is logical that attention is being paid to this by-product with a lower calcium content, obtained as a by-product in ore processing. In the Netherlands, blastfurnace slag is already widely used for production of blastfurnace cement (54% of the Dutch cement market). However, supersulphated cement contains less portland clinker than blastfurnace cement (2% compared with 30~ m/m), which means it requires less primary calcium. Further, it contains rather much calciumsulphate (I0 to 15% m/m), which the Dutch fertilizerindustry already produces in large quantities (2 million t/y) and which in the future will become available on a massive scale as a waste product in desulphurization of flue gases of coal-fired power plants. In the past, supersulphated cement was only used in a limited range of applications in the Netherlands, e.g. for sewerage works and in the chemical industry. It used to be imported from Belgium under the trade-name "Sealithor (R)", but recently disappeared from the Dutch market altogether. The principal technical reasons for the modest market share of supersulphated cement in the Netherlands and in other countries are: friability of the concrete skin, resulting in a dusty surface, the slow hardening of the concrete, especially at low temperatures, compared with portland cement, though not necessarily in comparison with blastfurnace cement.
-

With regard to o t h e r aspects, such as the energy costs of p r o d u c t i o n ,

Vol. I I , No. 3 SUPERSULPHATED CEMENT, BLAST FURNACESLAG, GYPSUM, STRENGTH


the physical-mechanical p r o p e r t i e s and the chemical r e s i s t a n c e of mortar and c o n c r e t e , supersulphated cement is c e r t a i n l y not i n f e r i o r to b l a s t f u r n a c e and p o r t l a n d cement. This paper is concerned notably w i t h the two negative aspects mentioned.

309

B A C K G R O U N D S
Reacting w i t h w a t e r , supersulphated cement does not y i e l d the same products as b l a s t f u r n a c e cement. For both types of cement, however, a h i g h l y a l k a l i n e medium is r e q u i r e d . In both cases p o r t l a n d c l i n k e r is normally used to provide t h i s a l k a l i n i t y . In the h i g h l y a l k a l i n e medium, d i f f u s i o n of ions can take place and d i s i n t e g r a t i o n of the s i l i c a t e - a l u m i n a t e s t r u c t u r e begins. The i n i t i a l s t r e n g t h of supersuiphated cement is due to the formation of e t t r i n g i t e , 3CaO.A1203.3CaSO4.32H20 w h i l e in a l a t e r stage the formation of calcium s i l i c a t e h y d r a t e s , CSH (I) and CSH (11), is important(I). The h y d r a u l i c i t y of b l a s t f u r n a c e slag depends on the glass s t r u c t u r e . The glass s t r u c t u r e is determined by the chemical composition of the s l a g , the tapping temperature and the v i s c o s i t y of the m e l t , the g r a n u l a t i o n temperature and the rate of g r a n u l a t l o n ( 2 , 3 ) . These parameters are c o r r e l a t e d . Thus, the v i s c o s i t y depends on the chemical compositions and the temperature. M i c r o s c o p i c a l l y , b l a s t f u r n a c e slags have a heterogeneous chemical composition. Slags w i t h the same chemical composition may d i f f e r in their microscopic structure. Most blastfurnace slags consists of socalled "mel ilite" glass (5), which is a mixture of akermanite (C2MS 2) and gehlenite (C2AS) . It appears that there is a close relation between the hydraulicity of the slag and the quantities of akermanite andgehlenite which are crystallized out when the slag is heated(3).
The optimum glass structure of the blastfurnace slag with a view to the strength development seems to be different for supersulphated cement and blastfurnace cement. However, research on this point is generally restricted to determination of the optimum (macroscopic) chemical composition(6,7). Other factors determining the glass structure are only marginally, if at all, considered in the studies carried out so far. The optimum chemical compositions for supersulphated cement stated in the literature should therefore be treated with some reserve. The pulverization of the concrete skin is the result of a reaction with carbondioxide gas, CO 2. During the initial setting and further hardening, C0 2 can be taken up in the water of the cement paste, so that the r a t h e r small a l k a l i n e b u f f e r in the form of a few percent of c l i n k e r is soon e l i m i n a t e d . The ground slag is no longer a c t i v a t e d then and remains unhydrated. The formation of a f r i a b l e skin in the course of cement h y d r a t i o n can be prevented by b l o c k i n g the p e n e t r a t i o n of ambient a i r f o r some time. This can be done by submerging the concrete or by leaving i t in the forms. The former is not always p o s s i b l e , and the l a t t e r is o f t e n o b j e c t i o n a b l e f o r economic reasons. On the basis of these c o n s i d e r a t i o n s , i t was decided in the study under review to g r i n d the supersulphated cement r e l a t i v e l y f i n e ( s p e c i f i c surface ca. 500 m2/kg).

310 J. B i j e n , E. Ni~l

Vol. I I ,

No. 3

Enlargement of the specific surface will raise the rate of the cement-water reaction. This again will reduce the negative effect of absorption of CO 2 in the water. COMPOSITION OF BASIC MATERIALS AND CEMENTS The blastfurnace slags examined came from blastfurnace works in the Netherlands and neighbouring countries. The chemical composition and origin are stated in table I. The samples of Dutch blastfurnace slags are different in that one sample consisted of granulated wet slag, while the other was a mixture of granulated dried slags (dry) of a composition averaged over a certain period. Table I also shows the chemical composition of the portland clinker used and the supersulphated reference cement (Sealithor R). Fluorogypsum(anhydrite), CaS04, and phosphogypsum (calciumsulphate di-hydrate), CaSO4.2H20 , were used as calciumsulphate source. Fluorogypsumis a by-product obtained in HF production, and phosphogypsum is obtained in the production of phosphoric acid. Composition and origin are stated in table 2.
TABLE I .

Chemical Composition Portland Clinker and Analysis


A Insoluble

and O r i g i n of Granulated B l a s t f u r n a c e Slags, SuperSulphated Reference Cement

Foreign
B C D

Dutch
E F

Portland clinker

Sealithor
(R)

in acid Loss on ignition CaO SiO2 Al203 MgO Fe203 TiO 2 K20 Na20 SO 3 S as SO 3

% % % % % % % % % % % %

0,74 -2,10 43,20 35,23 12,50 3,50 0,50 0,78 0,98 0,66 0,22 0,06

D,46 -2,03 43,61 34,17 11,05 5,86 0,99 0,18 0,56 0,69 0,10 0,21

0,62 -1,46 40,97 40,21 8,12 7,88 0,60 0,0 0,58 0,51 0,057 0,12

0,79 -1,35 40,18 40,15 7,04 9,90 0,59 0,0 0,70 0,41 0,13 0,10

0,28 -I,30 35,49 31,95 14,21 II,33 1,8 0,72 0,79 0,54 0,15 0,02

0,60 -0,76 35,44 31,67 16,27 11,08 0,69 1,20 0,77 0,61 0,12 0,01

0,66 1,15 63,31 25,18 4,67 1,26 1,39 0,0 0,81 0,25 0,225 n.d.

0,48 -0,90 40,55 29,04 11,05 4,75 1,44 0,83 0,97 0,69 7,36 0,13

Total excl. loss on ignition %

97,53

97,42

99,67

99,20

96,38

97,86

97,10

96,81

Vol. I I , No. 3 SUPERSULPHATED CEMENT, BLAST FURNACE SLAG, GYPSUM, STRENGTH TA~E 2. Composition of Chemical Gypsum

311

F I uorogy ps um (anhydri re)

Phosphogypsum

Free moisture (45oc) Bound water (45-215oc) r e l . to total weight r e l . to dry weight Sulphate (SO3)
rel. to t o t a l

% m/m

0,10 0,36 0,36 57,40 57,67 13,7

30,50 13,62 19,60 31,59 56,53 3,4

% m/m % m/m % m/m

weight

rel. to dry weight pH


Composition acc. to ASTM C 471:
Free moisture

% m/m

% m/m

0,1 1,7 96,2

30,50 65,10 2,3

CaSO4.2H20 CaS04

Because i t was found that the use of phosphogypsum led to a very considerable retardation of the cement hardening process, the gypsum was s p l i t into a coarse and a fine fraction in a hydrocyclone. Most of the phosphate and the fluorides, which cause this delay are present in the fine fraction. The coarse fraction amounted to 70% of the gypsum, the fine fraction to 30%. In the coarse fraction, 86% m/m of the particles was larger than 75 ~m. The total phosphate i . e . P205 content of this fraction, relative to the dry weight was 0.50% m/m, the proportion of phosphate soluble in saturated gypsum water was 0.19% m/m; the total fluorine content (as F) was 0.203% m/m, and the proportion of the fluorine soluble in saturated gypsum water was 0.018% m/m. After the separation in the hydrocyclone, the coarse fraction of the acid phosphogypsum had a pH of 5.1. With about 0.5% m/m Ca(OH)2, relative to the dry gypsum weight the coarse fraction was given the same pH as the fluorogypsum (pH=13.7). When the slags, gypsum and portland clinker had been ground, another quantity of 0.1% m/m Ca(OH)2 was added, so that the pH of this cement became the same as that of the cement activated with anhydrite (pH=12.8). The phosphogypsum probably contained incorporated acid components.
The S e a l i t h o r cement c o n t a i n e d o n l y a n h y d r i t e . The s l a g s , gypsum and c l i n k e r were mixed as s t a t e d in a b a l l m i l l .
R

in t a b l e 3, and ground

312 J. Bijen, E. Niel


TABLE 3. Composition of Various Cements

Vol. I I , No. 3

Cement symbol

Type of slag

Slag content

Gypsum content Clinker content % m/m 15 fluorogypsum 15 " 15 15 15 15 15 " " " " " % m/m 2 2 2 2 2 2 5 2

% m/m A
B

Specific surface (Blaine) m2/kg 530 513 509 538 519 530 522 540

foreign

83 83 83 83

C
D

E F FK 5 Fphos ph o

Dutch F F

83 83 80 83

Sealithor R (commercially available cement) Sealithor R fine ground

79

15 phosphogypsum coarse fraction (dry) 14 anhydrite

407

Sfine

79

14

"

522

The cements used for reference are portland cement A (PoA) and blastfurnace cement A (HoA). These cements meet the requirements of the Dutch standard NEN 3550. MECHANICAL STRENGTH DEVELOPMENT

Exper imenta l The start and the end of the cement binding process (Vicat) and the normal consistency were determined in accordance with the Dutch standard N 493. The mechanical strength tests were performed in accordance with the Dutch standard NEN 3072. Prisms of sand-cement mortar (3:1), 4 x 4 x 16 cm, were stored under plastic film for one day at 20C. Then the forms were removed and the prisms were stored under water at a temperature of 20oc. In order to ascertain the effect of the temperature, tests were also carried out at 5C. To determine the effect of water reduction, 3% m/m of Melment L 10 (A 20% aqueous solution of a sulphonated melamine formaldehyde resin) was added to cement F (see table 3); the water-cement factor was reduced and the workability was kept equal to that of the cement without a water reductor.

V01.

II,

No. 3 SUPERSULPHATED CEMENT, BLAST FURNACE SLAG, GYPSUM, STRENGTH

313

With supersulphated cement F and with commercially available cements, c o n c r e t e was p r e p a r e d f o r e x a m i n a t i o n of the comoressive strength development. The c o n c r e t e was made w i t h 320 k g / m 3 c e m e n t , and had a w a t e r - c e m e n t f a c t o r o f 0 . 4 8 . The f o r m s w e r e r e m o v e d f r o m t h e c o n c r e t e cubes a f t e r 3 d a y s . The c u b e s w e r e s t o r e d a t 20C a n d R . H . o f 100%.

Resvlts The s t a r t and the end of the binding process, the normal consistency and the dimensional s t a b i l i t y are stated in table 4. The mechanical strength development is represented in the figures I-7. Table 5 shows the results of the concrete tests. TABLE 4. Binding Time, Normal Consistency and Dimensional S t a b i l i t y of Cement Pastes

FK5

Fphos pho

Sfine

PoA

HoA

.,u,~D:n~:nstart

E
~

E i.~
--

E
~

E i~
--

E ~
~r~

E ~
N

E iJ~
~

E LP~
--

E ~
~

E co
~

E Lt%

............
I

termination

E ~

T ........

T....... E r.-.

= - ' - : .... : ............. E E E la%

= ..... E

~ ......

co

Z ......

---

Normal

consis~

tency
watercement rat ~ ~ ~ ~. ~ N ~ ~ ~ N. ~ ~. ~ N N N. o~ ~. ~ ~. ~ ~. r.. N

Dimensional stability ChateIier m m TABLE 5. Compressive Strength of Concrete (MPa) Compressive s t r e n g t h after Concrete wi th Supersul phated cement S 9,8 35,8 55,6 57,2
Concrete with Supersul phated cement F

3 7 27 57

days days days days

14,9 38,0 53,4 58,2

314 J. Bijen, E. Ni~l

Vol. I I ,

No. 3

4.3. Discussion Cements A-F and S Cement A and cement F on the basis of Dutch slags show the fastest initial strength development and also have, apart from the commercially available reference sunersulphated cements, the highest compressive strength after 28 and 56 days (fig.'s I and 2).
compressive strength [MPa] 80. I
0 B
,-J C /

,.t
-"

6o

i I
* s / /

...4

FIG. I. Compressive strength development of mortars with super sulphated cements A-F and S as a function of time.

14

28

56

The bending strength after 28 and 56 days is about the same for all the cements. The loss of bending stress strength is probably connected with the conversion of 3CaO.A1203.3CaSO4.321120(ettringite) into EaO.A1203 .CaSO 4. 12H20. With cements on the basis of blastfurnace slags and calciumsulphate, this loss of strength is not unusual, and either a recovery sets in after 6 to 12 months, or the strength stabilizes(9).
18- bending strength [MPa]
16

14 12'
1o

8 6

/A
I ; .f i ii7 i ., .,

FIG. 2. Bending strength development of mortar with super sulphated cements A-F and S as a function of time.

'~P

~.--t,.. [dsys]

Vol. I I , No. 3 SUPERSULPHATED CEMENT, BLAST FURNACE SLAG, GYPSUM, STRENGTH


Fluoro~ynsum - ohosphogypsum Phosphogypsum causes a retardation of the binding process compared with fluorogypsum (anhydrite). The start of the binding process is retarded by about 20 hours compared w i t h the fluorogypsum (see t a b l e 4). The r e t a r d a t i o n which a l s o appears from f i g . 3 and f i g . 4, is caused by
Compcesllve i t r e n g t h [ M P I ]

315

@...:y~.@
F ~ FksF 3%mllt ..'" ,/ ." ." . . . " ~ " /

6O

G F fosfo
. s

FIG. 3. Compressive strength development of mortar with cements F and reference cements as a function of time.

.~"

. " "

. -..'" '/ /
20

...f

.- / . . / _ . , . . < ~

---,,-

----" "" / i ..A'"/,~"..... ,,;-;~-''-

/;< :~ /

14

28

56

the f l u o r i d e s and w a t e r - s o l u b l e phosphates which are present :n the phosphogypsum. Although these substances are not present in large q u a n t i t i e s , they s t i l l cause a considerable r e t a r d a t i o n owing to the hiqh gypsum and low c l i n k e r content compared w i t h p o r t l a n d cement. A h i ~ e r p r o p o r t i o n of phosphate and f l u o r i n e w i l l have to be e x t r a c t e d from the phosphogypsum to make i t s u i t a b l e f o r use in supersulphGted cement. Another cause of the r e t a r d a t i o n may be that the gTD;um has to be a p p l i e d in the form of a n h y d r i t e .
18 16
.o 14

bending strength [MPa}


...o~.. .....
""...

12-

10FIG. 4. Bending s t r e n g t h development of mortar w i t h cements F and reference cements as a f u n c t i o n of time.


.

/...#.."
I.." , l.'" / l: /
/ "'

.p'~/ / /

o ~

"

/ v ~... r;" 2 -

8. 6.

- 7---".-'~.- - - ' ~ ..-~..~ I ..,~:.::~" ,

#D.'/
"/

~,,-,o
~ PoA

4.

2'
0

~ t!.~" ,,

"

t i m [a,y,]

316

Vol.

II,

No. 3

J. Bijen, E. Ni~l
Clinker content An increase in clinker content from 2 to 5% m/m (FK ) has a negative effect on the initial strength development (fig.'s 53 and 4). This is in agreement with the observations of Tanaka et al (6). Comparison with reference cement Cements E and F on the basis of Dutch slags have a good overall strength development at 20C, at least as good as that of the reference cements portland cement A and blastfurnace cement A. The commercially available supersulphated cement S has a Ibwer initial strength development, but reaches a higher compressive strength after 56 days. Cements E and F come in class B (cement with a high initial strength), in accordance both with the old Dutch standard N 491 and the new standard NEN 3550. Grinding fineness A higher grinding fineness enhances the rate of initial strength development and reduces the setting time. This appears from the measurement data for cement S and the finer cement Sfine; see fig.'s 5 and 6, and table 4. Water reducer With identical workability, addition of 3% m/m of Me lment L 10 relative to the cement weight, results in a 30% water reduction. Although a retardation of the setting process was observed, both the initial strength and the mechanical strength after 28 and 56 days are higher than when no water reducer is used; see fig.'s 3-6, cements F and F 3% Melment.

50-

compressive strength [ MPa]


o

.ss.:'

/0

46"

I
.~" ""

"
/
f

/
/

42"

o
38-

o
3430. 26"
d

.."""//
4 P

22" 18'

...'"~
f ,

.'

./'/
J

FIG. 5. Initial strength development o f m o r t a r w i t h cements A and F and r e f e r e n c e cements.

/' ~) 0 i~ (~
A

14.

lO
6

F F 3% m l l m l n t S S fl|n PoA MoA

Vol. I I , No. 3 SUPERSULPHATED CEMENT, BLAST FURNACE SLAG, GYPSUM, STRENGTH


1@ bending strength [ M P l ]
16
A F .."

317

14
0

Ir 3 % mek~eRt S S flirt

. .'"

12

FIG. 6. I n i t i a l bending strength development of mortar with cements A and F and reference cements.

8.

S
J..'" ~7 i /~.<'~. _. s ~ ." "

""

4-

-""

2-

.~y..-

--,.-t,m

[d.~]

Effect of temperature Fig. 7 is a graphic representation of the compressive strength development of cement F and the reference cements, portland A and blastfurnace A, hardened under water at 5 and at 20C. The loss of compressive strength of mortar hardened at 5oc compared with mortar hardened at 20oc is r e l a t i v e l y largest f o r supersu]phated cement F.
70compressive strength[MPa]

p
60 F

~r SO~

PoA
HoA = 200C

r 7

SC

/
40" .O

FIG. 7. Compressive strength development of mortar wlth supersulphated cement F, b l a s t furnace cement and portland A cement, hardened at 20 and 50C as a function of time.

30"

/ /
20'

~/~//,,
10'

/ /-//
/

..,. [d,,,] ;, 2'8 s'6

318 J. Bijen, E. Ni~l

Vol.

II,

No. i~

In an absolute sense, however, the hardening process at 5C is not slower than that of blastfurnace cement at the same temperature. Portland cement A shows the fastest strength development at 5C. Compressive strength development of concrete The compressive strength development of concrete to that of the mortar (fig. I) FRIABLE SKIN Experimental The thickness of the soft surface layer was measured with application of a method developed by Tanaka et al (6). In this method a small steel drill, as sketched in fig. 8, is placed on the concrete surface and rotated 30 times with a pressure of 300 g. The penetration depth is a measure of the degree of friability. The accuracy is * 0.05 mm. The test specimens were prepared as described in the paragraph on mechanical strength development. In order to approximate the practice conditions as much as possible, the specimens were taken out of the forms after 2 days and stored in the air at 20C or 5C and a R.H. of 100 or 60%. The penetration depth was measured after 7 days and after 2 months. The compressive strength and the bending strength were also measured after 7 days. In order to limit the range of the test, a number of cements were selected on the basis of mechanical strength data. Besides the reference cements, cement F was selected, because it had the best strength development, and cement A because it had the best strength development of the cements with no Dutch slags. The effect of the clinker content was examined by comparison of cement F (2% m/m of clinker) with cement FK5 (5% m/m of clinker). Melment L 10 was used as water reducer and a commonly used curing compound on a paraffin basis was added in order to ascertain their effect. Surface hardness tests were performed on concrete made with cement F. The concrete obtained 320 kg/m3 cement, and the water-cement factor was 0.48. After removal of the forms (after 3 days), p a r l o r the test specimens were stored in an air-conditioned room at 20C and a R.H. of 100%, the rest in the open air. During the testing period, the outdoor temperature varied from -3 to + 15oc, and the weather was alternately dry and wet. Results The results are shown in table 6. No essential differences were found between after 7 days and after 2 months.

(table 5) is analogous

the penetration

depths

Discussion Cements A and F, and reference cements at 20C Cement A gives a larger penetration depth than cement F after 7 days, which is in agreement with the results of the mechanical strength tests. The penetration depth with cement F is about equal to that with portland cement A, while with blastfurnace cement the depth

Vol. I I , No. 3 SUPERSULPHATED CEMENT, BLAST FURNACE SLAG, GYPSUM, STRENGTH TABLE 6. Results of Skin Pulverization Test Setting conditions after form removal Cement Temperature R e l a t i v e Humidity C
A

319

Curing Penetration Compound d e ~ t h a f t e r 7 days mm


-

7 days compressive strength MPa 33,8 37,3 36,1 27,3 44,9 64,0 45,4 31,6 40,8 18,9 25,2 27,7 3,2 37,1 9,7

% 100 100 100 60 I00 100 100 60 60 I00 I00 100


100

7 days bending stress strength MPa 10,6 7,1 10,5 5,3 8,8 13,7 11 ,6 5,7 6,4 4,5 8,4 7,5 0,6 7,7 1,4

20 20 20 20 20 20 20 20 20 5 20 20
5

0,55 0,20 0,60 1,00 0,20 0,15 0,50 0,55 0,25 0,80 0,75 0,60 I ,30 0,30 0,80
. . . . . . . . . . . . . . . . . . . . . . . . .

A 3% Me lment A A F F 3% Me lment F F F F FK5 S


S

yes yes yes yes -

S fine S fine
. . . . . . . . . . . . . . . .

20 5
. I . . . . I

100 100
. . . . . . . . . . . .

Po-A Po-A Po-A Po-A Ho-A Ho-A Ho-A Ho-A

20 20 20 5 20 20 20 5

100 100 60 I00 I00 100 60 I00

yes yes yes yes

0,25 0,50 0,30 0,35 0,60 0,75 0,85 0,95

31,1 23,7 23,4 11,7 26,0 21,4 20,2 7,1

7,3 6,1 4,4 2,8 7,1 9,1 4,1 2,4

is g r e a t e r and about the same as the depth measured f o r supersulphated cement A. A lower r e l a t i v e humidity only r e s u l t s in a minor increase in the p e n e t r a t i o n depth f o r cement F. The negative e f f e c t of lowering the r e l a t i v e humidity is more pronounced in the reduced compressive s t r e n g t h and bending s t r e n g t h a f t e r 7 days. The same is observed in t e s t s w i t h curing compound. C l i n k e r content Cement w i t h 5% p o r t l a n d c l i n k e r appears to give a g r e a t e r p e n e t r a t i o n depth than cement with 2~ portland clinker. This is in contrast with observations of Tanaka et al (6), who conclude that a higher clinker content gives a somewhat higher surface hardness. Evidently, the

320 J. B i j e n , E. Niel

Vol. I I ,

No. 3

higher initial mechanical strength (fig.'s 3 and 4) and the short period prior to the start of the setting process (table 4) are decisive. Another cause might be that the grinding fineness of the slag is lower with 5% clinker than with 2%. Blastfurnace slag is less easily ground than portland clinker, and the two substances were ground in combination. Grinding fineness The effect of a higher grinding fineness appears from a comparison of the degree of skin friability of concrete made with the commercially available supersulphated cement S, and of concrete made with cement of a higher grinding fineness, Sfine. The finer cement gives a lower degree of skin friability.

Water reducer As expected, lowering of the water-cement f a c t o r has a favourable e f f e c t on the degree of skin f r i a b i l i t y . Cement A w i t h 30% water reduction gives the same d r i l l p e n e t r a t i o n depth as cement F as such.
Curing compound The curing compound used had in all cases a negative effect on the concrete surface hardness; apparently, the paraffin, interferes with the water-cement reaction. In the case of cement F, when hardened at 20oc and a R.H. of 60%, it could moreover be concluded that the compressive strength and the bending strength are affected, while the contrary would be expected. Effect of the temperature Lowering of the hardening temperature from 20 to 5oc results in a relatively high increase in the degree of skin pulverization in the case of cement F. The penetration depth after 7 days is greater than that for portland cement A (0.80 versus 0.35 mm), but a little smaller than in the case of blastfurnace cement A (0.95 mm). Portland cement A is rather insensitive to temperature decreases as regards the degree of skin pulverization. In the case of blastfurnace cement, the low compressive and bending strengths after 7 days at 20oc are remarkable; these values are more than two times lower than for the concrete hardened under water. The cause of this is not understood.

Concrete surface hardness The penetration depth in cement F concrete (see table 7) stored in the open air is somewhat greater than for the same concrete stored indoors at 20oc and a R.H. of 1O0%. The difference is small, though. Neither the measurements, nor visual inspection reveal much difference with the mortar tests (table 6). To obtain a well-founded answer to the question whether the surface hardness might also be affected as a result of carbonation of cement hydration products, notably ettingite (2), an additional study will be carried out.
CONCLUSIONS Raw materials As a raw material for production of supersulphated cement, the Dutch blastfurnace slags came out best in our tests, both in terms of mechanical strength development and in terms of skin friability. The Dutch phosphogypsum caused a considerable retardation of the

Vol. I I , No. 3 S U P E R S U L P H A T E D CEMENT, BLAST FURNACE SLAG, GYPSUM, STRENGTH

321

TABLE 7. Results of Skin Pulverization Test on Concrete made with Cement F; Penetration Depth in r a m
storage c o n d i t i o n s Age 20C 7 days 28 days 56 days 100% R.H. 0,20 0,15 0,15 outdoors -3 vs.+15 C 0,25 0,20 0,35

O.Scm

5.5m

1~4m

FIG. 8.

D r i l l used f o r t,~sting o f skin p u l v e r i z a t ion


'

l~cm

'i

74m

s e t t i n g process compared w i t h fluorogypsum ( a n h y d r i t e ) . The phosphate and f l u o r i d e content o f the phosphogypsum w i l l probably have to be reduced to make i t a s u i t a b l e component f o r supersulphated cement. Mechanical s t r e n g t h Supersulphated cement c o n s i s t i n g of a mixture of 83% m/m of Dutch b l a s t f u r n a c e slag, 15% m/m o f fluorogypsum ( a n h y d r i t e ) and 2% m/m o f p o r t l a n d c l i n k e r , which mixture is ground to a s p e c i f i c surface o f 500 m2/kg, meets the requirements f o r class B (cements w i t h a high i n i t i a l s t r e n g t h ) in accordance w i t h the Dutch standard NEN 3550. At a low temperature (5oc) the i n i t i a l s t r e n g t h o f t h i s supersulphated cement corresponds w i t h t h a t o f b l a s t f u r n a c e cement A. Increase o f the g r i n d i n g fineness enhances the i n i t i a l s t r e n g t h . The behaviour o f concrete appears to be analogous to t h a t of mortars. In supersulphated cement made w i t h Dutch b l a s t f u r n a c e slag, an increase of the c l i n k e r content to 5~ m/m has a negative e f f e c t on the mechanical s t r e n g t h . Water reduction by means of a s o - c a l l e d s u p e r p l a s t i c i z e r c o n s i d e r a b l y improves the mechanical s t r e n g t h . Surface hardness The surface hardenss o f supersulphated cement made w i t h Dutch slags and o f the above-mentioned composition, hardened in the open a l r at 20oc and a R.H. o f 60 or 100~, is higher than that o f b l a s t f u r n a c e cement and about equal to that o f p o r t l a n d cement A. At 5C and aR.H.of 100%, the surface hardness is lower than t h a t o f p o r t l a n d cement A, and s l i g h t l y higher than t h a t of b l a s t f u r n a c e cement A. Increasing o f the s p e c i f i c surface improves the surface hardness. Measured over a period o f 2 months, no s i g n i f i c a n t d i f f e r e n c e between mortar and concrete is found. The surface hardness of supersuiphated cement made w i t h Dutch b l a s t f u r n a c e slags and 5% m/m p o r t l a n d c l i n k e r is lower than when 2% m/m p o r t l a n d c l i n k e r is used. Water r e d u c t i o n improves the surface hardness. Continued research

322
J. Bijen, E. Ni~l

Vol. I I ,

No.

Further studies on supersu]phated cement are performed on: optimization of the composition the effect of separate or combined grinding of slags, clinker and anhydrite - the effect of carbonation of cementhydration products on the strength - corrosion of reinforcement steel.
-

A C K N O W L E D G E M E N T W e thank the Dutch Minister of Public Health and Environmental Protection for sponsoring this study.

R E F E R E N C E S I. R.W. Nurse, Slag cements, The chemistry of cements, vol. 2 ed. H.F.W. Taylor, Academic Press, London (1964) pp 36-66. 2. F. Schr~der, Slags and slag cement, Proceedings of the V-International Symposium on Cement Chemistry, Tokyo (1968) vol IV pp 140-199. 3. V.I. Satarin, Slag portland cement, Proceedings of the VIInternational Symposium on Cement Chemistry, Moscow (1974). Principal Paper, pp 1-51.

4. H. Busch, A. P e t z o l d , P r o p e r t i e s and behaviour of b l a s t furnace slags in r e l a t i o n to t h e i r heat t r e a t m e n t , Cement Wapno Gips, 27 (1972) pp 9-12, T r a n s l a t i o n B.R.E. L i b r a r y no 1718.
5. S. Solacolu, Die Bedeutung der thermischen Gleichgewichte des Systems MgO - CaO - Al20 ~ - SiO^ flir das Schmelzen und Granulieren der Hochofenschlacke, Zei~went- KaZlk - Gips 4 (1958) pp 125-137.

6. T. Tanaka, T. Sakai, I. Yamane, Zusammensetzung Japanischer Hochofenschlacken f ~ r S u l f a t h ~ t t e n z e m e n t e , Zement - Kalk , Gips 2 (1958) pp 50-55.
7. F. Keil, F.W. Locher, Hydraulischer Eigenschaften yon Gl~sern, Zement - Kalk - Gips 6 (1958) PF) 245-253. 8. F.M. Lea, The chemistry of cement and concrete, ed. 3, Edward Arnold Ltd., London (1970) pp 418-485. 9. M. Raverdy, Etude d'un liant ~ base phosphogypse et de laitier, Bull. Lias. Labo. Ponts et Chauss. Nov. (1978) pp 69-77.