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    T h e H y d r a t i o n o f D e n t a l C e m e n t sALAN D . WILSON, JOHN M . PADDON a n d STEPHEN CRISPL a b o r a t o r y o f t h e G o v e r n m e n t C h e m i s t , C o r n w a l l H o u s e , L o n d o n S E 1 , E n g l a n dA s t u d y was made o f t h e h y d r a t i o n o f d e n t a l c e -m e n t s , w a t e r b e i n g c l a s s i f i e d as " n o n - e v a p o r a b l e "a n d " e v a p o r a b l e " . T h e r a t i o o f t h e s e two t y p e so f w a t e r wa s f o u n d t o v a r y g r e a t l y among d i f -f e r e n t cement t y p e s , b e i n g l e s s e r i n z i n c o x i d e a n di o n i c p o l y m e r cements a n d g r e a t e r i n i o n - l e a c h a b l eg l a s s a n d p h o s p h o r i c a c i d c e m e n t s . T h e cementw i t h t h e l e a s t " n o n - e v a p o r a b l e " w a t e r , i . e . , s h o w -i n g l e a s t h y d r a t i o n ( t h e z i n c p o l y c a r b o x y l a t ec e m e n t ) , h a d t h e l o w e s t s t r e n g t h a n d m o d u l u s a n dt h e g r e a t e s t d e f o r m a t i o n a t f a i l u r e . A l i n e a r r e l a -t i o n s h i p was f o u n d t o e x i s t b e t w e e n s t r e n g t h a n dt h e d e g r e e o f h y d r a t i o n o f d e n t a l c e m e n t s . A l l t h ecements were f o u n d t o b e c o m e more h i g h l y h y -d r a t e d a n d s t r o n g e r as t h e y a g e d .J D e n t R e s 5 8 ( 3 ) : 1 0 6 5 -1 0 7 1 , M a r c h 1 9 7 9Th e g e n e r a l m e c h a n i s m o f cement f o r m a t i o ni n d e n t a l cements can b e r e p r e s e n t e d as ana c i d - b a s e r e a c t i o n b e t w e e n a proton d o n a t -i n g l i q u i d a n d a powder w h i c h a c t s as ab a s e . A s a l t h y d r o g e l i s f o r m e d w h i c h b i n d st h e u n r e a c t e d p o w d e r p a r t i c la c e m e n t i t i o u s mass. Th er e a c t i o n may s i m p l y b e repre

    MO + H2A =powder l i q u i d s a l t hF o r c o n v e n i e n c e o f r e p ]o x i d e c a t i o n a n d t h e l i q u i d

    a s b e i n g d i v a l e n t . I n f a c t , Fs e n t p h o s p h o r i c or p o l y a c rM c an r e p r e s e n t A l as w e l l a( T h e s i l i c a , s o d i u m a n d f l u cc e m e n t s b a s e d on i o n - l e a c hi g n o r e d , s i n c e t h e y d o not at i a l f e a t u r e s o f t h e r e a c t i o ng a r d t h e powder a s a p r o v i d ea n d t h e l i q u i d as an a c c e p t (( F i g . 1 ) .T h e s e a c i d - b a s e r e a c t i o nt o b e f a r r e m o v e d f r o m P cw h i c h s e t s b y c o m p l e x h y d r aH o w e v e r , i t i s known t h a tt h e s e t t i n g t i m e a n d c o m p r e :p h o s p h a t e - b o n d e d cements z

    f e c t e d b y t h e w a t e r c o n t e n t o f t h e l i q u i d 2 ' 3 .A g a i n , a l t h o u g h d e n t a l c e m e n t s d e v e l o pt h e i r s t r e n g t h r a p i d l y a f t e r m i x i n g , s t r e n g t hc o n t i n u e s t o b e s l o w l y d e v e l o p e d f o r s e v e r a lm o n t h s . 4 - 6 T h e s e o b s e r v a t i o n s s u g g e s t t h a tt h e i n i t i a l a c i d - b a s e r e a c t i o n i s f o l l o w e d by as l o w e r process, s u c h a s t h e h y d r a t i o n o fr e a c t i o n p r o d u c t s .

    I n o r d e r t o a s c e r t a i n i f t h e r e was a h y -d r a t i o n phenomenon, a s t u d y was made o ft h e c o n d i t i o n o f w a t e r i n f o u r d i f f e r e n td e n t a l c e m e n t s : z i n c p h o s p h a t e , z i n c p o l y -c a r b o x y l a t e , s i l i c a t e a n d g l a s s - i o n o m e r . W a -t e r was c l a s s i f i e d i n t o " e v a p o r a b l e " a n d" n o n - e v a p o r a b l e " , a n d t h e e f f e c t o f a g i n gon t h e amounts c o n t a i n e d i n d e n t a l c e m e n t swas s t u d i e d .

    M a t e r i a l s a n d m e t h o d s .l e s t o g e t h e r i n t o Four b r a n d s o f d e n t a l c e m e n t , e a c h o f ag e n e r i c s e t t i n g d i f f e r e n t t y p e , w e r e s e l ec t e d f o r t h i s s t u d y :: s e n t e d thus: a d e n t a l s i l i c a t e c e m e n t ( S u p e r S y n t r e x * ) ,a z i n c p h o s p h a t e cement ( D e T r e y ' s Z i n c * ) ,MA +H20 a glass-ionomer cement (ASPA IV**), and

    l y d r o g e l a z i n c p o l y c a r b o x y l a t e cement ( P o l y F * ) .resnttin,the Cementswerepreparedunderstandard

    a n i o n a r e t a k e n ISO conditions of 23 I C and 50 5%i o A m ay r e p r e t r e l a t i v e h u m i d i t y . The d e n t a l s i l i c a t e ce-r y l i c a c i d s , a n d ment and the zinc phosphate cement werelicM C a n mixed u s i n g t h e s t a n d a r d t e c h n i q u e appro-~ s Zn, Mg orCa.) r i n e c o n t e n t o f p r i a t e t o e a c h a s d e s c r i b e d i n t h e I n t e r n a -L a b l e g l a s s e s are t i o n a l S t a n d a r d s O r g a n i z a t i o n ' s s p e c i f i c a t i o n sa f f e c t the essen- (ISO/R 1 5 6 5 a n d ISO/R 1 5 6 6 , r e s p e c t i v e l y ) .L f ) One e s s r e - Th e o t h e r c e m e n t s were m i x e d u s i n g t h ee r One may r e n dental s i l i c a t e cement technique. Theo r o f t h e s e i o n s p o w d e r / l i q u i d r a t i o u s e d w a s r e c o r d e d .E v a p o r a b l e w a t e r d e t e r m i n a t i o n s werecements appear performed ( i n d u p l i c a t e ) on cement d i s c s: ) r t l a n d cement ( 2 0 mm d i a m e t e r x 1 . 5 mm t h i c k ) w h i c hItioneactions1 h a d b e e n s t o r e d a t 37C i n s e a l e d c o n t a i n e r st i n e a r t i o n l s r f o r various times: 3 0 m i n , 4 h an d 3 40 h .s s i v e s t a r t i c u h a r f,, L . . , M". 16 .ss9&L"L,s s i v e s t r e n g t h o fa r e critically af- * A m a l g a m a t e d D e n t a l C o m p a n y , L o n d o n , E n -

    g l a n d* * L a b o r a t o r y o f t h e G o v e r n m e n t C h e m i s t ,L o n d o n , E n g l a n d .1 0 6 5

    R e c e i v e d f o r p u b l i c a t i o n N o v e m b e r 2 8 , 1 9 7 7 .A c c e p t e d f o r p u b l i c a t i o n J u n e 5 , 1 9 7 8 .

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    1 0 6 6 WILSONETAL.

    a c i d l i q u i d ( p r o t o n,IA d o n o r )

    ( d i s p l a c e d c a t i o n s M+ * MAm a t r i xs a l t g e lp o w d e r p a r t i d e

    b a s i c / a m p h o t e r i c m e t a l o x i d e( p r o t o n a c c e p t o r )F i g . l . - S c h e m a t i c r e p r e s e n t a t i o n o f t h e s e t t i n g r e a c t i o n i n d e n t a l c e m e n t s .

    T h e s e cement d i s c s were f o r m e d b y p l a c i n gt h e f r e s h l y m i x e d p a s t e i n a b r a s s r i n g ( i n -t e r n a l d i m e n s i o n s 2 0 mm d i a m e t e r x 1 . 5mm h i g h ) , h e l d i n a r e s t r a i n i n g f o r m e r ,p l a c e d on a s h e e t o f p o l y e t h y l e n e b a c k e d b ya s t a i n l e s s s t e e l p l a t e . Th e mould was c l o s e db y a s i m i l a r p o l y e t h y l e n e c o v e r e d s t a i n l e s ss t e e l p l a t e , a n d t h e w h o l e a s s e m b l y wasc l a m p e d t o g e t h e r . I n o r d e r t o o b t a i n f i g u r e s

    f o r zero t i m e , cement l i q u i d s were m i x e dw i t h f i n e l y g r o u n d q u a r t z powder t o f o r m as i m u l a t e d cement p a s t e .E v a p o r a b l e w a t e r was r e m o v e d b y p l a c i n ga w e i g h e d cement d i s c i n a d e s i c c a t o r c o n -t a i n i n g a n h y d r o u s m a g n e s i u m p e r c h l o r a t e ,w h i c h was c o n t i n u o u s l y e v a c u a t e d t o 1 0mm Hg pressure. T h i s process was c o n t i n u e du n t i l t h e cement d i s c a t t a i n e d c o n s t a n t

    TABLE 1COMPOSITION ( % m / m ) O F DENTAL CEMENT L I Q U I D SS i l i c a t e C e m e n t Z i n c P h o s p h a t e C e m e n tS u p e r S y n t r e x De T r e y ' s Z i n c

    T o t a l p h o s p h a t e 4 8 . 8 6 1 . 7( a s H 3 P O 4 )A 1 3 + 1 . 6 3 . 1Z n 2 + 6 . 1H2P04- ( c a l c ) 3 5 . 3 3 3 . 4f r e e H3PO4 ( c a i c ) 1 3 . 1 2 7 . 9H20 ( c a l c ) 4 3 . 9 3 5 . 5

    G l a s s - l o n o m e r C e m e n t Z i n c P o l y c a r b o x y l a t e C e m e n tASPA I V P o l y FP o l y a c i d 4 7 . 5 * 4 2 . 6 * *T a r t a r i c a c i d 5 . 0H20 ( c a l c ) 4 7 . 5 5 7 . 4

    * 2 : 1 p o l y ( a c r y l i c a c i d / i t a c o n i c a c i d )* * p o l y ( a c r y l i c a c i d )

    JDent R e s M a r c h 1 9 7 9

    4

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    HYDRA TION O F DENTAL CEMENTS

    W a t e r i n D e n t a l C e m e n t s

    E0 l ; w

    o L " mm".....L[L.AL,':,__? U 1 Eila1W 1'.1F ' .F i g . 2 . - N o n - e v a p o r a b l e a n d e v a p o r a b l e w a t e r p r e s e n t i n d e n t a l c e m e n t s o f v a r i o u s a g e s .

    TABLE 2WATER CONTENT OF DENTAL CEMENTSZ i n c P h o s p h a t e Z i n cC a r b o x y l a t e I o nDe T r e y ' s Z i n c P o l y F AS

    G l a s sn o m e r' P A I V

    S i l i c a t eS u p e r S y n t r e x

    P o w d e r / L i q u i d 3 . 4 2 . 4 3 . 0 4 . 0r a t i o g / m lL i q u i d d e n s i t y 1 . 6 9 1 . 1 8 1 . 1 0 1 . 5 5P o w d e r / L i q u i d 2 . 0 0 2 . 0 0 2 . 7 2 2 . 5 8r a t i o g / gW a t e r c o n t e n t * 1 1 . 9 1 9 . 2 1 2 . 7 1 3 . 8 +( e x c l u d i n g r e a c t i o nw a t e r )R e a c t i o n w a t e r * * 4 . 6 1 . 7 1 . 8 2 . 8T o t a l W a t e r 1 6 . 5 2 0 . 9 1 4 . 5 1 6 . 6

    * C a l c u l a t e d f r o m t h e c h e m i c a l c o m p o s i t i o n o f t h e c o m p o n e n t s o f t h e c e m e n t , b u t n o t i n c l u d i n g r e a c -t i o n w a t e r .* * C a l c u l a t e d a s s u m i n g c o m p l e t i o n o f t h e r e a c t i o n w i t h t h e f o r m a t i o n o f n e u t r a l s a l t s .+ A l l o w i n g f o r 2 . 2 % w a t e r i n t h e p o w d e r .

    N u E _ o p b WA

    V o l . 5 8 N o . 3 1 0 6 7

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    J D e n t R e s M a r c h 1 9 7 9

    TABLE 3EFFECT OF CEMENT AGE ON HYDRATION STATE* AND PROPERTIESZ i n c P h o s p h a t e Z i n c P o l y c a r b o x y l a t e G l a s s - I o n o m e r S i l i c a t e- De T r e y ' s Z i n c P o l y F ASPA I V S u p e r S y n t r e x

    0 3 0 3 4 0 0 3 0 3 4 0 0 3 0 3 4 0 0 3 0 3 4 0m i n m i n 4 h h m i n m i n 4 h h m i n m i n 4 h h m i n m i n 4 h hN o n -e v a p o r a b l e :E v a p o r a b l ew a t e r 0 . 0 0 . 5 4 0 . 6 0 0 . 7 2 0 . 0 9 0 . 0 5 0 . 0 7 0 . 2 2 0 . 0 0 . 4 2 0 . 5 4 1 . 2 0 0 . 0 0 . 6 8 0 . 8 9 1 . 0 8C o m p r e s s i v es t r e n g t h( N / m m 2 ) - 9 3 1 4 1 1 5 0 - 4 0 6 2 7 5 - 7 1 1 4 6 2 7 5 - 1 1 7 2 0 1 2 5 2Y i e l ds t r e n g t h( N / m m 2 ) - 4 3 1 0 8 1 2 0 - 1 8 3 0 4 5 - 2 4 9 2 2 2 5 - 5 5 1 9 0 2 3 0M o d u l u s o fe l a s t i c i t y , E( 1 0 3 xN / m m 2 ) - 1 1 . 7 1 3 . 5 1 3 . 0 - 3 . 5 5 . 1 7 . 3 - 5 . 1 8 . 8 1 8 . 0 - 1 1 . 2 2 0 . 4 2 1 . 3P l a s t i c S t r a i na t f r a c t u r e , a( x 1 0 - 3 ) - 2 . 3 0 . 7 8 0 . 2 2 - 1 0 . 1 6 . 6 7 2 . 8 7 - 2 3 5 . 8 6 0 . 9 5 - 0 . 8 8 0 . 1 6 0 . 2 0

    * U n d e r s e a l e d c o n d i t i o n s a t 3 7 Cw e i g h t . A t a l l t i m e s t h e cement d i s c wasc o n t a i n e d i n a w e i g h i n g b o t t l e so t h a t i tc o u l d b e i s o l a t e d f r o m a m b i e n t c o n d i t i o n sd u r i n g w e i g h i n g a n d t r a n s f e r t o a n d f r o m t h ed e s i c c a t o r .T h e p e r c e n t a g e o f e v a p o r a b l e w a t e r i sg i v e n b y t h e e q u a t i o n :

    W i -W f x100W.

    W h e r e , W i i s t h e i n i t i a l w e i g h t o f t h e cement-d i s c , a n d Wf i s t h e f i n a l w e i g h t a f t e r d e s i c -c a t i o n .Th e t o t a l w a t e r c o n t e n t o f e a c h d e n t a lcement was c a l c u l a t e d f r o m i t s c h e m i c a lc o m p o s i t i o n ( T a b l e 1 ) . I n a d d i t i o n t o t h ew a t e r c o n t a i n e d i n t h e l i q u i d , d u e a l l o w a n c ewas made f o r w a t e r g e n e r a t e d d u r i n g t h ecourse o f t h e r e a c t i o n e x c e p t i n t h e cases o ft h e u n r e a c t i v e q u a r t z / l i q u i d s p a s t e s . R e a c -t i o n w a t e r was c a l c u l a t e d f r o m t h e a n i o n i cc o n t e n t o f t h e l i q u i d , . a s s u m i n g t h a t a l la n i o n s i n t h e l i q u i d c o m b i n e d w i t h m e t a li o n s f r o m t h e powder t o f o r m a n e u t r a l s a l t .R e s u l t s o f t h e s e c a l c u l a t i o n s are p r e s e n t e d i nT a b l e 2 .M e c h a n i c a l p r o p e r t i e s were d e t e r m i n e d

    u s i n g cement c y l i n d e r s ( 1 2 mm l o n g x 6mm d i a m e t e r ) . A f t e r p r e p a r a t i o n t h e s e c e -m e nt c y l i n d e r s w e r e s t o r e d i n l i q u i d p a r a f -f i n c o n t a i n e d i n s t o p p e r e d b o t t l e s a t 370Cf o r 3 0 m i n , 4 h o r 3 4 0 h b e f o r e t e s t i n g . Th ec y l i n d e r s w e r e c r u s h e d i n a n e l e c t r o - m e c h a n -i c a l t e s t i n g m a c h i n e * a t a c r o s s h e a d s p e e do f 1 m m / m i n . S t r e s s a n d p l a s t i c s t r a i n a tf r a c t u r e , y i e l d s t r e s s a n d t h e m o d u l u s o fe l a s t i c i t y i n c o m p r e s s i o n w e r e t a k e n o r c a l -c u l a t e d f r o m t h e s t r e s s - s t r a i n c u r v e s c o r -r e c t e d f o r t h e m a c h i n e c o n s t a n t .R e s u l t s a n d d i s c u s s i o n .

    R e s u l t s o b t a i n e d f o r t h e " n o n - e v a p o r a b l e "a n d " e v a p o r a b l e " w a t e r c o n t e n t s o f t h e f o u rd e n t a l c e m e n t t y p e s a t v a r i o u s t i m e s a r ep r e s e n t e d a s h i s t o g r a m s i n F i g u r e 2 . T h et o t a l w a t e r c o n t e n t o f t h e q u a r t z l i q u i dp a s t e s w h i c h s i m u l a t e c e m e n t p a s t e s a t z e r ot i m e s i s l e s s , s i n c e no r e a c t i o n w a t e r i s p r o -d u c e d . Th e r a t i o o f n o n - e v a p o r a b l e w a t e rt o e v a p o r a b l e w a t e r , w h i c h r e p r e s e n t s t h ee x t e n t o f h y d r a t i o n o f c e m e n t s , i s g i v e n i nT a b l e 3 . Th e q u a r t z / l i q u i d p a s t e s w e r e f o u n dt o c o n t a i n no n o n - e v a p o r a b l e w a t e r . I n a l lc a s e s t h i s r a t i o w a s f o u n d t o i n c r e a s e a s t h ec e m e n t s a g e d , s h o w i n g t h a t a t y p e o f h y d r a -t i o n r e a c t i o n o c c u r s . T h i s r a t i o w a s a l s of o u n d t o v a r y g r e a t l y among t h e d i f f e r e n tt y p e s o f c e m e n t . C e r t a i n c o n c l u s i o n s may b e* I n s t r o n M o d e l T T C M , I n s t r o n , L t d . , H i g h W y -c o m b e , B u c k s , E n g l a n d

    1 0 6 8 WILSON ET A L .

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    d r a w n . M o s t o f t h e h y d r a t i o n r e a c t i o n t a k e sp l a c e i n t h e f i r s t 3 0 m i n , a n d t h e s a l t m a t r i c e so f t h e s e c e m e n t s p r o b a b l y p r e c i p i t a t e s a sh y d r a t e d f o r m s . I n g e n e r a l , z i n c o x i d e c e -m e n t s a r e l e s s h y d r a t e d t h a n t h o s e c e m e n t sb a s e d on i o n - l e a c h a b l e g l a s s e s , w h i l e t h ed e g r e e o f h y d r a t i o n o f p h o s p h a t e - b o n d e dc e m e n t s t e n d s t o b e h i g h e r t h a n t h a t o f c e -m e n t s c o n t a i n i n g h a r d l y a n y n o n - e v a p o r a b l ew a t e r .T h e e f f e c t o f t e m p e r a t u r e on t h e h y d r a -t i o n o f o n e t y p e o f d e n t a l c e m e n t , t h e g l a s s -i o n o m e r c e m e n t , i s s h o w n i n F i g u r e 3 . I n -c r e a s e i n t e m p e r a t u r e i s s e e n t o a c c e l e r a t et h e r a t e o f h y d r a t i o n .T h e r a t i o o f n o n - e v a p o r a b l e w a t e r t o e v a -p o r a b l e w a t e r p r e s e n t i n a c e m e n t i s r e l a t e dt o v a r i o u s m e c h a n i c a l p r o p e r t i e s i n T a b l e 3 .T h i s t a b l e s h o w s t h a t t h e d e g r e e o f h y d r a -t i o n o f a c e m e n t c o r r e l a t e s w i t h c o m p r e s s i v es t r e n g t h , y i e l d s t r e n g t h , m o d u l u s o f e l a s t i -c i t y a n d w i t h t h e i n v e r s e o f p l a s t i c s t r a i na t f a i l u r e . T h e s e t r e n d s a r e e x e m p l i f i e d b y

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    t h e g r e a t e s t m o d u l u s a n d s h o w t h e l e a s td e f o r m a t i o n a t f r a c t u r e . I n g e n e r a l , z i n co x i d e c e m e n t s a r e w e a k e r a n d l e s s h y d r a t e dt h a n i o n - l e a c h a b l e g l a s s c e m e n t s , a n d c e -m e n t s b a s e d o n p o l y c a r b o x y l i c a c i d a r ew e a k e r a n d l e s s h y d r a t e d t h a n t h o s e b a s e do n p h o s p h o r i c a c i d . T h e w e a k e s t a n d l e a s th y d r a t e d c e m e n t i s , t h u s , t h e z i n c p o l y c a r -b o x y l a t e c e m e n t . " E v a p o r a b l e " w a t e r a p -p e a r s t o a c t a s a p l a s t i c i z e r , f o r t h e z i n cp o l y c a r b o x y l a t e c e m e n t i s t h e m o s t p l a s t i co f a l l t h e c e m e n t s . Th e s t r e n g t h s o f d e n t a lc e m e n t s a r e d i r e c t l y r e l a t e d t o t h e r a t i o o f" n o n - e v a p o r a b l e " w a t e r t o " e v a p o r a b l e "w a t e r . T h e h y d r a t i o n o f d e n t a l c e m e n t s ,a n d t h u s t h e i r s t r e n g t h , i n c r e a s e s a s t h e ya g e .A c k n o w l e d g m e n t s .

    T h e a u t h o r s t h a n k t h e G o v e r n m e n tC h e m i s t , D r . H . E g a n , f o r p e r m i s s i o n t o c o n -t r i b u t e t h i s p a p e r . R e p r o d u c e d b y p e r m i s -

    s i o n o f t h e C o n t r o l l e r o f H e r B r i t a n n i c M a -j e s t y ' s S t a t i o n e r y O f f i c e .REFERENCES

    1 . L E A , F . M . : T h e C h e m i s t r y o f C e m e n t a n dC o n c r e t e , 3 r d e d . , E d w a r d A r n o l d , L o n d o n ,1 9 7 0 .2 . WORNER, H . K . a n d DOCKING, A . R . : D e n -t a l M a t e r i a l s i n t h e T r o p i c s . A u s t . D e n t . J .3 : 2 1 5 -2 29 , 1 9 5 8 .3 . W I L S O N , A . D . ; KENT, B . E . ; BATCHELOR,R . F . ; SCOTT, B . G . ; a n d L E W I S , B . G . : D e n t a lS i l i c a t e C e m e n t s : X I I . T h e R o l e o f W a t e r :J . D e n t . R e s . 4 9 : 3 0 7 - 3 1 4 , 1 9 7 0 .4 . PAFFENBARGER, G . C . ; SCHOONOVER, I . C .a n d SOUDER, W . : D e n t a l S i l i c a t e C e m e n t s :P h y s i c a l a n d C h e m i c a l P r o p e r t i e s a n d a S p e c i f i -c a t i o n , J . Am. D e n t . A s s o c . 2 5 : 3 1 - 8 7 , 1 9 3 8 .5 . C R I S P , S . ; L E W I S , B . G . ; a n d WILSON, A . D . :C h a r a c t e r i z a t i o n o f g l a s s - i o n o m e r c e m e n t s . 1 .L o n g t e r m h a r d n e s s a n d c o m p r e s s i v e s t r e n g t h ,J . D e n t . 4 : 1 6 2 - 1 6 6 , 1 9 7 6 .6 . PADDON, J . M ; a n d WILSON, A . D . : S t r e s sR e l a x a t i o n S t u d i e s o n D e n t a l M a t e r i a l s . 1 .D e n t a l C e m e n t s J . D e n t . 4 : 1 8 3 - 1 8 9 , 1 9 7 6 .

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