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

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.178 T. 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). ( w ) . Vrbos Vol.28. 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 . 0 2 2 at w/c r a t i o of 0.3%.2%. 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. 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.Yugoslav standard . 39. 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.7%.C8. 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 . 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.5. Matusinovic and N. 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 . 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 . 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. All experiments used a water/cement (w/c) r a t i o of 0. 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. 11. 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.0%.023. 40. 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 . Pula. 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 " . 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 .7. C r o a t i a . Fe203. 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 25°C 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. 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 r e s e a r c h are s h o w n in T a b l e 2. 23. *JUS . and 90 days. FeO. 4. 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. No. A1203.24. 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 .3. 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.

005 0.001 Setting time/s 16500 7330 1650 710 440 F M LINO 3 0.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. 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.23.No.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 .ALKALIMETAL SALTS.0005 0.Vol.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 . I SET ACCEI22ATORS.05 0. 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 . Alkali metal salts: times at 0.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.i F .01 0.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.

3 11.75 93. pH values 12.92 8.72 10.12 HAC 58.03 HAC + CsNO~ 8.15 10.08 HAC TABLE 5 mortars and HAC mortars made with Compressive HAC + NaNO~ 52.35 82.01% l i t h i u m salts in m i x i n g water.55 86.12 10.180 T.10 76.94 11.70 67. Mamsinovic and N.50 92.25 HAC 8.66 88.9 5.20 11.51 10.4 5. Time/ days 1 3 7 28 90 HAC + LiNO~ 49.72 11.32 7.92 8.12 10.77 HAC + KNO~ 7.35 10. No.97 84.65 10.01% alkali metal salts.99 9.15 HAC + CsNO~ 56.8 11.2 10.87 70.95 79.67 10.05 82.68 8.14 8.68 HAC + NaNO~ 7.44 8.10 11.4 6.6 5.29 88.60 96.36 28 90 C o m p r e s s i v e s t r e n g t h s of 0. Vrbos VoL 23.18 61.78 75.71 79.62 8.25 82.95 11.25 .09 62.4 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.42 64.62 63.30 10.30 9.45 66.85 85.91 strength/MPa HAC + RbNO~ 7.12 73.75 strength/MPa HAC + RbNO~ 55.73 HAC + KNO~ 53.88 10.01% Flexural HAC + LiNO I 7. 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. Time/ days 1 3 7 made with 0.90 91.

64 3.0 i0. With the fraction of 0.Vol. is formed.22 x . The principal hydraulic constituent in HAC is CaAl204 (CA).0 6. and their c o n v e r s i o n to Ca3A1206x6H20 (C3AH6) (12).0 1.65 43.5 1.93 8.96 6.1% setting occurs i m m e d i a t e l y by a d d i n g of LiNO~.12 18. the setting time decreases.0 20.0 15.KALIMETAL SALTS. With increasing the fraction of LiNO~.05% Li2CO3. After d i s s o c i a t i o n of CA.0 2.62 32.t e m p e r a t u r e dependency: the l o w .21 4.61 6.0 4.0 X X X X X X X 1.82 3.AI.65 8.96 12.88 7.77 48. 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 .87 30. The c o m p o s i t i o n of the hydration products shows a t i m e .5 3.37 4. 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). 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). C~AH6.11 3.95 7.33 20.93 2.0 3. The h y d r a t i o n process of CA is generally believed to occur through initial dissolution.42 2.12 4..15 2. but also Ca2Al2OsxSH20 (C2AHB).83 46. 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 0.19 2.5 5.44 3.56 X X X X X X X X X X X 1. 23.02 21.16 36.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%. 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 0.25 23.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.60 13.89 5.5 2.5 4.86 4.34 4.80 24.48 6.56 4.58 36. 1 SET ACCELERATORS. No.

thus e l i m i n a t i n g the i n d u c t i o n period.to -AI(6) c o n v e r s i o n is a b o u t to begin. 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). w h i l e Na ÷. 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. H o w e v e r . Matusinovic imdN. 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. 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. (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 . 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 .182 T.f o l d .c o o r d i n a t e d a l u m i n i u m . 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. No. CAHI0. W i t h o u t any a d d i t i v e . Of the ions studied. if f r a c t i o n of 0. at w h i c h p o i n t the A I ( 4 ) . S o l i d . the a c t i o n of l i t h i u m . 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 . Rb ÷.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 . and Cs ÷ w i l l f o r m the o c t a h e d r a l type (15). 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. Vrbos Vol. 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). K ÷.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. 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.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. 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 . 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. 23. Thus.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 (14). At a w/c r a t i o of 0. 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. 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. AH~ and C3AH 6 c o n t a i n 6 .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. C2AHs. 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 . D o u b l e et al. 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). 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.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. 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 . 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. 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.

l i t h i u m h a v i n g a d r a s t i c effect. 23. sulfide of and weak and very weak metaborate) have a acids linear . Figs. 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. Parameter Crystal Hydrated Hydration radii/nm radii/nm number Li 0. No. and e n t h a l p i e s of h y d r a t i o n . Alkaline lithium salts.340 25 530 Na 0. AIJfAIJ METAL SALTS.12 MPa. 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).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. 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 .148 0. 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. 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. TABLE metal 7 cations hydration numbers Hydration data on the a l k a l i (16).232 10 340 Rb 0.098 0. 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.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. 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 . 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. salts (hydroxide. ALUMINATE CEMENT 183 (Tables 2 and 3). 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.65 MPa. carbonate. 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. 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.Vol.228 315 Cs 0. 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. a l k a l i n e l i t h i u m salts.276 16 420 K 0.068 0.133 0. pH of the s o l u t i o n . A f t e r 4 h. 1 SET ACCELERATORS. 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.167 0.

A or) r-. Vrbos VoL 23. E . 1 Setting times of paste v_ss.2 Setting times of paste v__ss. -$ u~ E} L) Lt} 133 0 600 _ j s< cC Br~ ~ ' ~ ' ' / J 4O0 r SETTING TIME L t= 100"2599pH+1. pH of acid lithium salts.3t) 0 v 400 SETTING TIME 1 -O.2116 t=lO I00 I I I I0 II 12 pilaf 0.059pH + 3.. Matusinovlc and N.. 1 E 0 r- u3 I.001°/o tithium salt in mixing water FIG. u') QU..5 0. No.184 T.0935 200 l I I 55 pilaf 6 6. . pH for alkaline lithium salts..001°/o [ithium sort in mixing water FIG.

10. anorg. 3. 12 (1988). Chem. H . Nr. The acids salts (bromide.Currell. ii. H..R. 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. 648851.Crahan. 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.. F e r d i n a n d Enke Verlag.2116 w h e r e t is the setting time. I .Brauer.Juza and P.Luong. anorg. Z. 79 (1954). S . 14. 2. ALKALI METAL SALTS. H.600. Soc. Patent 3. Deutschland. 4.Parsonage.Grzeskowlak.Novlnson. U. References "Fluldizlng M o d l l n g Material for M a n u f a c t u r i n g Cores and Molds and a M e t h o d Therefor". 23. Symp. Patent 3.. 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. Concr. 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. Third Int. G. 5. Z.665. T.. allgem. G .D. 7. Ceram. Res. !. Stuttgart.Mayer.203.Laurer.R. C h e m i s t r y of Cement. 73 (1984). Cement and Concrete A s s o c i a t i o n (1954). Res.S. J. J. 287. 1 SET ACCELERATORS. R o d g e r and D. Am. L o n d o n 1952. Concr.. 8. 9. R. Cem.S.Juza and P. R. U. No. 275. Mater. T. nitrate. Inst. M i d g l e y and J.Parker. "Verfahren zur V e r k ~ r z u n g der A b b l n d e z e l t von T o n e r d e z e m e n t e n " R e l c h s p a t e n t a m t Patentschrlft. Proc. R.826. 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. Concr. allgem.Vol. 420 (1987). p512 (5). I. B.I.Double. 6. 72 (ii) 2136 (1989). T . Chem. "Setting and H a r d e n i n g of Alumlnous Cement".. .Laurer. Z. chloride. N o v i n s o n and J. 113 (1956). H a n d b u c h der Praparatlven A n o r g a n l s c h e Chemle. Cem.Eckert and T. (1960). t e c h n o l o g y and informatics of Croatia.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. Am.

.WelIs.F. Oxford Press.Bailar. J.Emeleus. F. Properties and Materials. 1 12.. Matuslnovlc and N. Interscience Publishers.Muller..). Prentice-Hall.Wilkinson. 17. Volume i.186 T..K.F. London (1962). (1972). A. Advanced Inorganic Chemistry: A Comprehensive Text.M. J. New York (1973).Mehta. Vrbos Vol. R.Rettel. Edward Arnold Ltd. 57.C.Nyholm and A. A. London (1976). No. New York. 15. W. 14. The Chemisty of Cement and Concrete.Trontman-Dickenson (Eds. Concrete Structure. 152 (1984). 23. P. Engelwood Cliffs. New Jersey (1986). Comprehensive Inorganic Chemistry.Cotton and G. F. 16.A..Lea.Gessner and G.Scheler. Magn. D. H. 13. Pergamon Press. Reson.J. Structural Inorganic Chemistry.

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