Manja, K Srinivasa

Narayanan, T K Nambi

Rao, A Srinivasa

IACS Institutional Repository

N O T EIndian J. Phys. 7 0 A  ( 2 ) ,  2 6 5 - 2 6 8  ( 1 9 9 6 )I J P  A- an international journalU ltrasonic studies on poly-m ethyl m ethacrylate in  ethyl m ethyl ketoneV i j a y a l a k s h m i  R  S a n y a ] ,  T  K  N a m b i  N a r a y a n a n ,  K  S r in i v a s a  M a n j a  a n d  A  S r in i v a s a  R a o *Raman School ol Physics, Pondicheny University, Kalapet.Pondicherry-605 014. IndiaRei eived 31 May 1995. an opted 30 (h tober 1905Abstract : Ultrasonic velocity studies have been carried out in solutions ot poly­methylmethacrylate (PMMA) in ethyl methyl ketone (FMK) in the concentration range 0-V/7 by weight, at ladio frequency of 2 MH/ at three diffeicnt temperatures 293 K, 297 K and 301 K The increase in ultiasomc velocity with increase ol PMMA concentration is attributed to the segment-segment interaction which causes molecular association between PMMA and EMKKeywords : Ultrasonic parameters, PMMA, EMKPACS No. : 43.35 BfI n  r e c e n t  y e a r s ,  e x t e n s i v e  u s e  o f  p o l y m e r i c  m a t e r i a l s  i n  t e c h n o l o g y  h a s  n e c e s s ia t e d  t h e  s t u d y  o f  m o l e c u l a r  i n t e r a c t i o n s  o f  p o l y m e r s  w i t h  s o lv e n t s .  A c o u s t i c s  w a s  u s e d  a s  a  t o o l  t o  s t u d y  t h e  p h y s i c a l  p r o p e r t i e s  o f  t h e  p o l y m e r s .  T h e  p r e s e n t  w o r k  w a s  u n d e r t a k e n  w i t h  t h e  v i e w  o f  s t u d y i n g  t h e  m o l e c u l a r  i n t e r a c t i o n  o t  s o lu t i o n s  o f  P M M A  i n  E M K  a t  s e v e r a l  c o n c e n t r a t i o n s  a n d  t e m p e r a t u r e s .P M M A  w a s  d i s s o l v e d  b y  s w i r l i n g  i n  t h e  s o l v e n t  E M K  f o r  s o lu t e  c o n c e n t r a t i o n s  o f  0 - 3 %  b y  w e i g h t .  P r e c a u t i o n s  w e r e  t a k e n  t o  a v o i d  v a r i o u s  t y p e s  o t  p o s s ib le  d e g r a d a t i o n  [ 1 ] .  T h e  m e a s u r e m e n t s  o f  u l t r a s o n i c  v e l o c i t y  w e r e  c a r r ie d  o u t  a t  t h r e e  d i f f e r e n t  t e m p e r a t u r e s .U l t r a s o n i c  t i m e  l n t e r v a l o m e t e r  ( M o d e l - U T I  1 0 1 ,  I n n o v a t i v e  I n s t r u m e n t s ,  H y d e r a b a d )  w a s  e m p l o y e d  t o  m e a s u r e  u l t r a s o n i c  v e l o c i t y  i n  s a m p le  s o l u t i o n s  a t  f i x e d  f r e q u e n c y  2  M H z .  T h e  a c c u r a c y  o f  t h e  m e a s u r e d  v a lu e s  o f  u l t r a s o n i c  v e lo c i t i e s  is  2  p a r t s  i n  1 0 4 . T h e  d e n s i t y  w a s  m e a s u r e d  u s in g  s p e c i f i c  g r a v i t y  b o t t l e .  T h e  v i s c o s i t y  w a s  m e a s u r e d  u s in g  a n  O s t w a l d ' s  v i s c o m e t e r .  T h e  a c c u r a c y  o f  d e n s i t y  a n d  v i s c o s i t y  m e a s u r e m e n t s  a r e  ±  2  p a r t s  i n  1 0 4 a n d  0 . 1 % .  A l l  t h e  a b o v e  m e a s u r e m e n t s  w e r e  c a r r i e d  o u t  a t  t h r e e  d i f f e r e n t* To whom correspondence is to be addressed. ©  1996,1 A C S266 V ija y a la k sh m i R  S a n y a l e t a lt e m p e r a t u r e s  2 9 3  K ,  2 9 7  K  a n d  3 0 1  K  w i t h  a n  a c c u r a c y  o f  ±  0 . 1  ° C .  C o n s t a n t  t e m p e r a t u r e  o f  t h e  s a m p l e  w a s  m a i n t a i n e d  b y  c i r c u l a t i n g  w a t e r  f r o m  a  t h e r m o s t a t i c a l l y  c o n t r o l l e d  w a t e r  b a t h .  T h e  m o l e c u l a r  w e i g h t  o f  P M M A  is  5 2 , 0 8 3 8  d e t e r m i n e d  b y  v i s c o s i t y  m e t h o d  [ 2 ] .T h e  d e n s i t y  ( p ) ,  u l t r a s o n i c  v e l o c i t y  ( C )  a n d  s h e a r  v i s c o s i t y  ( 7 ] )  w e r e  m e a s u r e d  a t  t h r e e  d i f f e r e n t  t e m p e r a t u r e s .  U s i n g  t h e  a b o v e  p a r a m e t e r s ,  R a o 's  n u m b e r  ( / ? )  a n d  a d i a b a t i c  c o m p r e s s i b i l i t y  ( / ? )  w e r e  c a l c u l a t e d  u s i n g  t h e  f o r m u l af t  =  ( c 2p r '  ( i )C ' V  =  R ( 2 )w h e r e  C =  u l t r a s o n i c  v e l o c i t y ,7j  =  v i s c o s i t y  o f  w a t e r ,  p  =  d e n s i t y  o f  t h e  s o l u t i o n ,V =  m o l a r  v o l u m e  o f  t h e  s o l u t i o n .T h e  v a l u e s  o f  t h e  a b o v e  p a r a m e t e r s  a r e  t a b u l a t e d  i n  T a b l e s  1 - 3 .Tabic 1. Ultrasonic and lelated parameters for solution of PM M A m EM K  at 301 KConcentration Density of Ultrasonic Adiabatic Shear Rao’s(Wt7r) solution p  kg.!)’ 'velocity C ms-1compressibility fis x IO_10N -|m2viscosity 77 Nsur 2numberR x 10^0  0 0 0 800 73 1170 9 9 1081 0 3688 6  85400 . 2 0 0 801 46 1173 7 9.0574 0.5634 6.85490  500 802 47 1175 0 9 0256 0 6614 6.84890 700 803 48 1177.1 8 9820 0.7986 6  84441 (X)0 807 24 1179 3 8 9075 1 2720 6  81402  (X)0 814.31 1181 9 8 7903 4 1060 6  76263 (XX) 821 19 1188.7 8 6175 1 0  2126 67187Table 2. Ultrasonic and related parameters for solution of PM M A in EM K  at 297 KConcentration Density of Ultrasonic Adiabatic Shear Rao's(wt%) solution p velocity C compressibility viscosity numberkgm--1 ms" 1 f t x  IO-|0 N“'ni2 rf N sn f2 K x  I010.000 802.52 1183 8 8 8917 0.4333 6.86550  2 0 0 804.14 1186 2 8  8379 0.7030 6.85260.500 805.29 1188.1 8  7971 0.7868 6.85020 700 808.72 1191.7 8.7069 0.8942 6.82791.000 811.19 1194.3 8.6427 1.4184 6.81222 . 0 0 0 818.62 1197.4 8.5199 4.9463 6.75563.000 824.12 1 2 0 2 .2 8 3956 11.2315 6.7200I t  c a n  b e  s e e n  f r o m  t a b l e s  t h a t  u l t r a s o n i c  v e l o c i t y ,  a t  a l l  t e m p e r a t u r e s ,  g e n e r a l l y  i n c r e a s e s  w i t h  i n c r e a s e  i n  s o l u t e  c o n c e n t r a t i o n  a n d  f o r  a n y  p a r t i c u l a r  s o l u t e  c o n c e n t r a t i o n .U ltr a s o n ic  s tu d ie s  o n  p o ly (m e th y l  m e th a c r y la te )  in  e th y l  m e th y l  k e to n e  267t h e  u l t r a s o n i c  v e l o c i t y  d e c r e a s e s  w i t h  i n c r e a s e  o f  t e m p e r a t u r e .  T h e  a d i a b a t i c  c o m p r e s s i b i l i t y  d e c r e a s e s  w i t h  i n c r e a s e  o f  s o l u t e  c o n c e n t r a t i o n  a t  a l l  t e m p e r a t u r e s .  T h e  d e n s i t y  a n d  s h e a r  v i s c o s i t y  i n c r e a s e  w i t h  i n c r e a s e  i n  s o l u t e  c o n c e n t r a t i o n .Table 3. Ultrasonic and related parameters for solution of FM M A in EM K  at 293 KConcentration(wt%)Density of solution p  kgm~ 3Ultrasonic velocity C  ms" 1Adiabatic compressibility PBx  lO ^ b H m 2Shear viscosity rf NsnT2Rao's number R x 1030  0 0 0 804 58 1196 7 8 6792 0 4702 6.87240 . 2 0 0 805 5! 1199 0 8.6355 0 8295 6.86920  500 806 63 1200 4 8 6034 0 9429 6  86230  700 808 80 1202.3 8.5532 10355 6.84581 0 0 0 811 37 1204.2 8  4958 1.5808 6.82942 0 0 0 822 11 12104 8.3025 5.9722 675173 000 827 06 1217 5 8 1568 12.9601 6.7244T h e  g r a d u a l  i n c r e a s e  i n  u l t r a s o n i c  v e l o c i t y  w i t h  s o l u t e  c o n c e n t r a t i o n  a t  a l l  t e m p e r a t u r e s  m a y  b e  d u e  t o  a s s o c i a t i o n  b e t w e e n  s o l u t e  a n d  s o l v e j n t  m o l e c u l e s  i n  F M M A  i n  E M K .  A s  t h e  c o n c e n t r a t i o n  i n c r e a s e s ,  o n e  m a c r o m o l e c u l e  m a y  i n f l u e n c e  a n o t h e r  i n d i r e c t l y ,  b y  w a y  o f  m u t u a l  i n t e r a c t i o n .  I n  m o r e  c o n c e n t r a t e d  s o l u t i o n s  a n d  b u l k  p o l y m e r s ,  d i r e c t  s e g m e n t - s e g m e n t  i n t e r a c t i o n  e x i s t s  [ 3 ] .  I t  c a n  b e  s e e n  f r o m  t a b l e s  t h a t  i n c r e a s e  i n  t h e  u l t r a s o n i c  v e l o c i t y  i n  t h e  e n t i r e  s o l u t e  c o n c e n t r a t i o n  r a n g e  0 - 3 %  i s  a b o u t  2 0 . 8  m / s .  I t  h a s  b e e n  r e p o r t e d  t h a t  t h e  i n c r e a s e  i n  u l t r a s o n i c  v e l o c i t y  f o r  a  s i m i l a r  c o n c e n t r a t i o n  r a n g e  f o r  s o l u t i o n  o f  P V C  i n  D M F  [ 4 ]  i s  a b o u t  2 4 . 3  m / s  a n d  P V C  i n  c h l o r o b e n z e n e  | 5 J  i s  a b o u t  1 0  m / s .  S i n c e  t h e  o b s e r v e d  i n c r e a s e  i n  t h e  u l t r a s o n i c  v e l o c i t y  i n  t h e  s o l u t e  c o n c e n t r a t i o n  r a n g e  0 - 3 %  i n  t h e  p r e s e n t  s t u d y  i s  o f  t h e  s a m e  o r d e r ,  i t  c a n  b e  a s s u m e d  t h a t  t h e  c o n c l u s i o n  d r a w n  f o r  s o l u t i o n s  o f  P V C  i n  D M F  a n d  P V C  i n  C B  a r e  a p p l i c a b l e  t o  t h e  p r e s e n t  s t u d y .  T h e  v a n  d e r  W a a l ' s  i n t e r a c t i o n  m a y  b e  r e s p o n s i b l e  f o r  a s s o c i a t i o n  b e t w e e n  m o l e c u l e s  o f  P M M A  a n d  E M K  a t  l o w  s o l u t e  c o n c e n t r a t i o n s .  F o r  a n y  s o l u t e  c o n c e n t r a t i o n ,  t h e  u l t r a s o n i c  v e l o c i t y  d e c r e a s e s  w i t h  i n c r e a s e  i n  t e m p e r a t u r e  a n d  t h i s  m a y  b e  d u e  t o  w e a k e n i n g  o f  i n t e r m o l c c u l a r  f o r c e s  d u e  t o  t h e r m a l  e f f e c t s .  F u r t h e r  w o r k  w i l l  c o n f i r m  t h e  a b o v e  c o n c l u s i o n .  F r o m  T a b l e s  1 - 3 ,  i t  c a n  f u r t h e r  b e  s e e n  t h a t  t h e  s h e a r  v i s c o s i t y  g e n e r a l l y  i n c r e a s e s  w i t h  i n c r e a s e  i n  s o l u t e  c o n c e n t r a t i o n .  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Ultrasonic Studies on Poly-Methyl Methacrylate in Ethyl Methyl Ketone

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Ultrasonic Studies on Poly-Methyl Methacrylate in Ethyl Methyl Ketone

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