CEMENT and CONCRETE RESEARCH. Vol. 23, pp. 177-186, 1993. Printed in the USA. 0008-8846/93. $6.00+.00.

Copyright 1993 Pergamon Press Ltd.

ALKALI

METAL

SALTS

AS

SET ACCELERATORS

FOR

HIGH

ALUMINA

CEMENT

T . M a t u s i n o v i c and N.Vrbos U n i v e r s i t y of Zagreb D e p a r t m e n t of Chemical E n g i n e e r i n g and Technology Marulicev t r g 20, 41000 Zagreb, C r o a t i a

(Sef=eed) (Received Feb. 4; in fnudform March 4, 1992)

ABSTRACT

The effect of alkali metal salts on the setting time of high aluminia cement (HAC) has been studied. The influence of c o n c e n t r a t i o n of the salts, chemical nature of anion and the type of alkali metal cation have been investigated. The results of the research indicate that alkali metal salts are set accelerators of HAC. The lithium cation has more effect on the setting time than other alkali cations because of its ability to form tetrahedral symmetry while the others will form the octahedral type. L i t h i u m salts remove the n u c l e a t i o n barrier, caused by an initially fast precipitation. The influence of pH in mixing water is not important. The effect of hydroxyl group is greater than effect of other i n v e s t i g a t e d anions due to the replacement leading to a further centre for oxobridge formation. The l i t h i u m salts cause d e c r e a s i n g of flexural and compressive s t r e n g t h of H A C mortars but also cause the strength d e v e l o p m e n t at early ages.

Introduction

L i t h i u m salts have been reported as accelerating setting agents for alumina concretes in the patent literature(l-3). Parker r e p o r t e d that the setting time of HAC pastes could be influenced by a d d i t i o n of small amounts of m a n y materials. Double(4) and Currell(5) studied the c h e m i s t r y of hydration of HAC in the p r e s e n c e of accelerating and retarding admixtures. Novinson et ai.(7,8) i n v e s t i g a t e d the effects of lithium salts on r e f r a c t o r y mortars. In chemical terms, the mode of action of these admixtures is not well understood. In this paper alkali metal salts as set accelerators of HAC have been studied. The influence of c o n c e n t r a t i o n of the salts, chemical nature of anions and the type
177

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T. Matusinovic and N. Vrbos

Vol. 23. No. 1

of a l k a l i m e t a l c a t i o n s h a v e b e e n i n v e s t i g a t e d . T h e r e s e a r c h has b e e n c a r r i e d out to d e v e l o p r a p i d s e t t i n g and h a r d e n i n g m a t e r i a l s for the r e p a i r of c o n c r e t e . We have b e e n c o n d u c t i n g e x p e r i m e n t s to determine the optimal setting time and the strength of the m a t e r i a l s m a d e w i t h l i t h i u m salt a d m i x t u r e s .

Experimental

Methods

T h e h i g h a l u m i n a c e m e n t u s e d was a n o r m a l p r o d u c t i o n of " G i u l i o R e v e l a n t e " , Pula, C r o a t i a . T h e g e n e r a l a n a l y s i s of s u c h c e m e n t was: CaO, 40.2%, A1203, 39.0%, FeO, 4.3%, Fe203, 11.7%. T h e a d m i x t u r e s used were commercial Analar grade reagents dissolved in d e m i n e r a l i z e d w a t e r p r i o r to m i x i n g w i t h HAC. LizS a n d R b O H w e r e prepared in o u r l a b o r a t o r y (9-11). The s e t t i n g t i m e of HAC in d e p e n d e n c e of the pH of l i t h i u m salts in m i x i n g w a t e r has b e e n measured. T h e pH of e a c h s o l u t i o n w a s m e a s u r e d w i t h a s t a n d a r d g l a s s e l e c t r o d e . T h e e l e c t r o d e was c a l i b r a t e d w i t h b u f f e r s o l u t i o n at 25C at pH 4 a n d 9. The salt s o l u t i o n was p o u r e d into the b o w l a n d the HAC w e r e a d d e d to the water. T h e s e w e r e m i x e d t o g e t h e r b y means of m e c h a n i c stirrer for p r e s c r i b e d time intervals. All experiments used a water/cement (w/c) r a t i o of 0.24. T h e s e t t i n g time was determined using a modification of the JUS ~ m e t h o d B.C8.023. In o u r m o d i f i c a t i o n the p e n e t r a t i o n of the n e e d l e into h a r d e n i n g p a s t e was m e a s u r e d e v e r y 5 s e c o n d s due to e x t r e m e l y r a p i d setting time for l i t h i u m salt m o d i f i e d . The e x p e r i m e n t s were r e p e a t e d t h r e e times to o b t a i n r e l i a b l e s t a n d a r d d e v i a t i o n s a n d s t a t i s t i c a l means. For d e t e r m i n a t i o n of c o m p r e s s i v e a n d f l e x u r a l s t r e n g t h the s p e c i m e n s (40 x 40 x 160 mm) w e r e p r e p a r e d a c c o r d i n g to JUS B . C 8 . 0 2 2 at w/c r a t i o of 0.5. The s p e c i m e n s w e r e t e s t e d at the age of 1,3,7,28, and 90 days. T h r e e s p e c i m e n s w e r e t e s t e d for e a c h age. Results

T h e m e a s u r e m e n t of the i n f l u e n c e of d i f f e r e n t m a s s f r a c t i o n , ( w ) , of l i t h i u m n i t r a t e on the s e t t i n g t i m e of HAC has b e e n d o n e to c h o o s e the f r a c t i o n of the salt w h i c h can give a s e t t i n g t i m e c o n v e n i e n t for t h e r e s e a r c h . The r e s u l t s of the m e a s u r e m e n t are s h o w n in T a b l e i. The m e a s u r e m e n t s of the i n f l u e n c e of d i f f e r e n t a l k a l i m e t a l s a l t s on the s e t t i n g t i m e has b e e n made. The r e s u l t s of the r e s e a r c h are s h o w n in T a b l e 2. *JUS - Yugoslav standard

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SET ACCEI22ATORS,ALKALIMETAL SALTS,ALUMINATE CEMENT

179

Lithium

nitrate:

Comparison fractions.

TABLE 1 of s e t t i n g t i m e s

at d i f f e r e n t

mass

Lithium

salt

w(LiNO~)/% 0 0.0005 0.001

Setting

time/s

16500 7330 1650 710 440 F

M

LINO 3

0.005 0.01 0.05 0.i

F - s e t t i n g of HAC w i t h l i t h i u m n i t r a t e d u r i n g the m i x i n g t i m e M - s e t t i n g of HAC i m m e d i a t e l y by a d d i n g of the l i t h i u m n i t r a t e TABLE 2 C o m p a r i s o n of s e t t i n g fraction.

Alkali

metal

salts:

times

at 0.01% m a s s

Anions Cations Li Na K Rb Cs

OH-

S=

C03 =

Br"

CI-

NO3 =

SO Z

Setting 300 5140 7200 9140 iiii0 325 5620 7400 370 6300 7980 9260 11990

time/s 305 8940 10120 10930 11200 360 9720 10200 10680 11400 440 6480 7920 9360 11480 560 7800 8100 9300 11630

- dash

llne

indicates

that the c h e m i c a l salts have been

was

not a v a i l a b l e and the results are

The d i f f e r e n t l i t h i u m s h o w n in the T a b l e 3.

tested

Discussion

T h e r e s u l t s of the r e s e a r c h i n d i c a t e that a l k a l i m e t a l s a l t s are set a c c e l e r a t o r s of HAC. The d a t a in T a b l e 1 d e m o n s t r a t e t h a t L i N O 3 a c c e l e r a t e s the s e t t i n g time of HAC e v e n at the m a s s f r a c t i o n of

180

T. Mamsinovic and N. Vrbos

VoL 23. No. 1

Lithium

salts:

TABLE 3 C o m p a r i s o n of s e t t i n g times and pH of 0.01% l i t h i u m salts in m i x i n g water. pH values 12.3 11.8 11.2 10.4 6.4 5.9 5.6 5.4 Setting 300 325 370 390 560 440 360 305 time/s

Lithium LiOH Li~S

salt

Li2CO ~ LiBO 2 Li2SO 4 LiNO~ LiCI LiBr

TABLE 4 F l e x u r a l s t r e n g t h s of HAC m o r t a r s and HAC m o r t a r s alkali metal salts. Time/ days 1 3

7

made with

0.01%

Flexural HAC + LiNO I 7.32 7.92 8.99 9.65 10.68 HAC + NaNO~ 7.44 8.30 9.88 10.12 10.77 HAC + KNO~ 7.68 8.15 10.12 10.51 10.91

strength/MPa HAC + RbNO~ 7.92 8.35 10.30 10.72 11.03 HAC + CsNO~ 8.14 8.72 10.67 10.94 11.25 HAC 8.62 8.95 11.10 11.20 11.36

28 90

C o m p r e s s i v e s t r e n g t h s of 0.01% alkali metal salts. Time/ days 1 3 7 28 90 HAC + LiNO~ 49.18 61.87 70.10 76.25 82.08

HAC

TABLE 5 mortars

and

HAC

mortars

made

with

Compressive HAC + NaNO~ 52.09 62.12 73.71 79.85 85.73 HAC + KNO~ 53.62 63.78 75.05 82.29 88.75

strength/MPa HAC + RbNO~ 55.42 64.95 79.55 86.90 91.15 HAC + CsNO~ 56.45 66.35 82.66 88.75 93.12 HAC 58.70 67.97 84.50 92.60 96.25

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SET ACCELERATORS,AI.,KALIMETAL SALTS, ALUMINATECEMENT

181

TABLE 6 C o m p r e s s i v e and flexural strengths of HAC mortars and HAC mortars made w i t h 0.05% Li2CO3. Time/h C o m p r e s s i v e strength/MPa HAC HAC+ Li~CO 3 Flexural s t r e n g t h / M P A HAC HAC+ Li2CO 3

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 6.0 i0.0 15.0 20.0

X X X X X X X

1.82 3.86 4.89 5.93 8.96 12.60 13.12 18.33 20.02 21.25 23.87 30.62 32.16 36.56

X X X X X X X X

X X X

1.42 2.44 3.11

3.93

2.65 8.80 24.58 36.65 43.83 46.77 48.12

4.21 4.37 4.56 4.96 6.48 6.88 7.15

2.19 2.64 3.34 4.61 6.95 7.22

x - test could not be p e r f o r m e d because specimens were too soft to be removed from the mold 5xi0-4%. With increasing the fraction of LiNO~, the setting time decreases. With the fraction of 0.1% setting occurs i m m e d i a t e l y by a d d i n g of LiNO~. The principal hydraulic constituent in HAC is CaAl204 (CA). The h y d r a t i o n process of CA is generally believed to occur through initial dissolution, formation of a metastable gel and s u b s e q u e n t p r e c i p i t a t i o n p r i n c i p a l l y CaAI204xlOH20 (CAHI0), but also Ca2Al2OsxSH20 (C2AHB), and their c o n v e r s i o n to Ca3A1206x6H20 (C3AH6) (12). The c o m p o s i t i o n of the hydration products shows a t i m e - t e m p e r a t u r e dependency: the l o w - t e m p e r a t u r e hydration products (CAHI0) is t h e r m o d y n a m i c a l l y unstable e s p e c i a l l y in w a r m and humid storage c o n d i t i o n w h e n a more stable compound, C~AH6, is formed. L a b o r a t o r y and field experience with HAC concretes show that on p r o l o n g e d storage the hexagonal CAHI0 and C2AH 8 phases tend to convert to the cubic C3AH 6 (13). After d i s s o c i a t i o n of CA, the formed m e t a s t a b l e gel will acquire stability by c o n d e n s a t i o n of m o n o c o o r d i n a t e d OH groups linked to A1 to form oxobridges b e t w e e n

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T. Matusinovic imdN. Vrbos

Vol. 23, No. 1

two A1 c e n t e r s l e a d i n g to the c r y s t a l l i n e CAHI0 (6). To produce such an o x o b r i d g e s condensation structure it is n e c e s s a r y to b r i n g the OH g r o u p in a p o s i t i o n that a lone p a i r on the o x y g e n can o v e r l a p w i t h a d o r b i t a l of AI, r e s u l t i n g in the f o r m a t i o n of an o x o b r i d g e and a m o l e c u l e of w a t e r w h i c h w o u l d r e m a i n h y d r o g e n b o n d e d to the o x y g e n atom. S o l i d - s t a t e N M R d a t a i n d i c a t e that a l u m i n i u m in CA is e n t i r e l y 4c o o r d i n a t e d but the p r i n c i p a l h y d r a t i o n p r o d u c t s of CA, CAHI0, C2AHs, AH~ and C3AH 6 c o n t a i n 6 - c o o r d i n a t e d a l u m i n i u m . The 27AI N M R w o r k shows that the h y d r a t i o n of c a l c i u m a l u m i n a t e c e m e n t s p r o c e e d s as a c o n v e r s i o n of 4- to 6- f o l d - c o o r d i n a t e d a l u m i n i u m (14). In situ 2VAl N M R s t u d i e s of the h y d r a t i o n p r o c e s s w e r e c a r r i e d out on c e m e n t s a m p l e s h y d r a t e d w i t h d e m i n e r a l i z e d w a t e r and w i t h a s o l u t i o n of Li2CO 3 in d e m i n e r a l i z e d w a t e r (8). W i t h o u t any a d d i t i v e , the A1 c o n v e r s i o n s t a r t s o n l y a f t e r a p p r o x i m a t e l y 3-4 h i n d u c t i o n p e r i o d and a p p e a r s to end a f t e r 18-20 h. At a w/c r a t i o of 0.5 the f r a c t i o n of 4 - c o o r d i n a t e d a l u m i n i u m in the final p r o d u c t a m o u n t s to approximately 30% to 40% of the e n t i r e A1 content. The d a t a o b t a i n e d w i t h the a d d i t i v e are in s h a r p c o n t r a s t to the h y d r a t i o n w i t h d e m i n e r a l i z e d water, the c o n v e r s i o n of AI(4) to AI(6) s t a r t s i m m e d i a t e l y a f t e r mixing, if f r a c t i o n of 0.5% a q u e o u s l i t h i u m c a r b o n a t e s o l u t i o n is u s e d as the h y d r a t i o n medium. H o w e v e r , the rate constant of the a l u m i n i u m conversion process is w i t h i n e x p e r i m e n t a l error, i d e n t i c a l to that found in the a b s e n c e of the l i t h i u m a d d i t i v e . Thus, the a c t i o n of l i t h i u m - c o n t a i n i n g s e t t i n g a c c e l e r a t o r s is b a s e d on a s h o r t e n i n g of the i n d u c t i o n p e r i o d w h i l e h a v i n g no e f f e c t on the rate of the p h a s e t r a n s f o r m a t i o n p r o c e s s . The i n d u c t i o n p e r i o d d u r i n g the p r e c i p i t a t i o n of CAHI0 and C2AH 8 from a s u p e r s a t u r a t e d s o l u t i o n is a r e f l e c t i o n of the n u c l e a t i o n b a r r i e r to the f o r m a t i o n of t h e s e c o m p o u n d s . D o u b l e et al. (5) a t t r i b u t e the a c c e l e r a t i n g e f f e c t of l i t h i u m salts to a r e m o v a l of this n u c l e a t i o n b a r r i e r , c a u s e d by an i n i t i a l l y fast p r e c i p i t a t i o n of l i t h i u m h y d r o m e t a a l u m i n a t e . This c o m p o u n d is t h e n t h o u g h t to act as a h e t e r o g e n e o u s nucleation substrate, thus e l i m i n a t i n g the i n d u c t i o n period. This v i e w is e n t i r e l y c o m p a t i b l e w i t h N M R r e s u l t s p r e s e n t e d by N o v i n s o n (8), w h i c h i n d i c a t e that the a c c e l e r a t o r a f f e c t s o n l y the i n d u c t i o n but not the rate of p h a s e c o n v e r s i o n once the n u c l e a t i o n b a r r i e r has b e e n broken. The N M R r e s u l t s s u g g e s t f u r t h e r that the m e a s u r e m e n t s of s e t t i n g time a p p e a r s to be m o s t c l o s e l y r e l a t e d to the end of the i n d u c t i o n period, at w h i c h p o i n t the A I ( 4 ) - to -AI(6) c o n v e r s i o n is a b o u t to begin. The r e s u l t s of such a m e a s u r e m e n t in the p r e s e n t s t u d y p r o v e it. The o x o b r i d g e s c o n d e n s a t i o n s t r u c t u r e s w i l l be a f f e c t e d by a l k a l i m e t a l c a t i o n s f o r m i n g c o - o r d i n a t i o n l i n k a g e w i t h the h y d r o x y l groups. Of the ions studied, Li* s h o u l d be d i f f e r e n t in b e h a v i o u r from the o t h e r c a t i o n s b e c a u s e of the a b i l i t y to form t e t r a h e d r a l symmetry w i t h OH groups, w h i l e Na , K , Rb , and Cs w i l l f o r m the o c t a h e d r a l type (15). This is p r o v e d by our e x p e r i m e n t a l r e s u l t s

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SET ACCELERATORS, AIJfAIJ METAL SALTS, ALUMINATE CEMENT

183

(Tables 2 and 3), l i t h i u m h a v i n g a d r a s t i c effect, but d i f f e r e n c e s b e t w e e n the o t h e r c a t i o n s are not g r e a t and e x h i b i t a d e f i n i t i v e trend. T h e s e t t i n g t i m e of HAC w i t h the d e c r e a s e s in the f o l l o w i n g order:
Cs > Rb > K >

same

salts

of

alkali

metal

Na

>>

Li

The s e q u e n c e f o l l o w s the t r e n d of c r y s t a l radii, and e n t h a l p i e s of h y d r a t i o n . TABLE metal 7 cations

hydration numbers

Hydration

data

on the a l k a l i

(16).

Parameter Crystal Hydrated Hydration radii/nm radii/nm number

Li 0.068 0.340 25 530

Na 0.098 0.276 16 420

K 0.133 0.232 10 340

Rb 0.148 0.228 315

Cs 0.167 0.228 10 280

-AHh/kJ mol -l

T h e c o m p r e s s i v e s t r e n g t h of HAC m o r t a r s c o u l d not be m e a s u r e d w i t h i n 4 h o u r s b e c a u s e the s p e c i m e n s w e r e too soft to be r e m o v e d from the mold. A f t e r 4 h, w h e n the p e r i o d of i n d u c t i o n time e n d e d the s p e c i m e n s had the m i n i m a l c o m p r e s s i v e s t r e n g t h of 2.65 MPa. It can be s e e n from t a b l e 6 that t h e r e is a s u d d e n i n c r e a s e in s t r e n g t h for HAC m o r t a r s up to the age of 4 h. A f t e r 20 h HAC m o r t a r h a d a c o m p r e s s i v e s t r e n g t h of 48.12 MPa, a p p r o x i m a t e l y 50% v a l u e s of the i n f i n i t i v e c o m p r e s s i v e s t r e n g t h . HAC m o r t a r s w i t h l i t h i u m c a r b o n a t e s h o w e d a f t e r 30 m i n a c o m p r e s s i v e s t r e n g t h of 1.82 M P a and i n c r e a s e s r a p i d l y w i t h aging. T h e s e r e s u l t s s u p p o r t the r e s u l t s of r e s e a r c h m a d e by D o u b l e (5) as w e l l as N o v i n s o n (8). The results of the m e a s u r e m e n t s of c o m p r e s s i v e and flexural s t r e n g t h of a l k a l i m e t a l n i t r a t e s (Tables 4 and 5) s h o w t h a t a l k a l i m e t a l s a l t s d e c r e a s e the s t r e n g t h of HAC. It is a p p a r e n t that the s t r e n g t h i n c r e a s e s w i t h an i n c r e a s e in age of H A C m o r t a r s as w e l l as HAC m o r t a r s w i t h a l k a l i m e t a l salts. T h e i n v e s t i g a t e d l i t h i u m salts can be c l a s s i f i e d in t w o g r o u p s , a l k a l i n e l i t h i u m salts, from l i t h i u m h y d r o x i d e and v e r y w e a k a c i d s (K^ ~ i0 -7 mol dm -3) and a c i d l i t h i u m salts d e r i v e d f r o m s t r o n g and v e r y s t r o n g a c i d s (K A ~ 10 -2 mol dm -3) (17). The d a t a w e r e p l o t t e d as s e t t i n g times v_ss. pH of the s o l u t i o n . Figs. 1 a n d 2 i l l u s t r a t e the r e l a t i o n s h i p b e t w e e n s e t t i n g t i m e and pH for a l k a l i n e salts and a c i d salts. Alkaline lithium salts, salts (hydroxide, carbonate, sulfide of and weak and very weak metaborate) have a acids linear

184

T. Matusinovlc and N. Vrbos

VoL 23, No. 1

E
0
r-

u3 I;3t) 0 v

400

SETTING TIME 1 -O.059pH + 3.2116 t=lO

I00
I I I

I0

II

12

pilaf

0.001/o tithium salt in mixing water

FIG. 1 Setting times of paste v_ss. pH for alkaline lithium salts.

u') QU,

E
.,,.,

or) r-.

-$
u~

E} L) Lt} 133 0

600
_ j

s<
cC Br~ ~ ' ~ ' ' / J

4O0

r SETTING TIME L t= 100"2599pH+1,0935

200

55 pilaf

6 6.5 0.001/o [ithium sort in mixing water

FIG.2 Setting times of paste v__ss, pH of acid lithium salts.

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SET ACCELERATORS, ALKALI METAL SALTS. ALUMINATE CEMENT

185

e x p r e s s i o n w i t h a negative slope and follow the equation

t = 1 0 -'sgPs +

3.2116

w h e r e t is the setting time. The acids salts (bromide, chloride, nitrate, sulphate) follow a linear plot w l t h a positive slope and seem to obey the e q u a t i o n
t = 1 0 0"2599pH + 1.0935

The effect of hydroxyl group is greater than the effect of the other i n v e s t i g a t e d anions due to the replacement of m o l e c u l e s H20 by hydroxyl groups in the A1 environment leading to a further centre for o x o b r i d g e formation. The other investigated anions have a lesser effect w h i l e they substitute OH groups in the c o o r d i n a t i o n sphere of AI, w h i c h leads to the removal of a hydroxyl group n e c e s s a r y In the process of oxolation. Acknowledqment

The authors a c k n o w l e d g e financial support from the M i n i s t r y of science, t e c h n o l o g y and informatics of Croatia.
References

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