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So	
  called	
  ternary	
  systems	
  are	
  being	
  used	
  for	
  several	
  decades	
  by	
  the	
  construction	
  
chemistry	
  predominantly	
  in	
  making	
  self-­‐leveling	
  screeds	
  ,	
  under-­‐	
  and	
  over	
  
layments	
  –	
  non	
  shrink	
  grouts	
  ,	
  repair	
  mortars	
  etc.	
  
They	
  are	
  based	
  on	
  mixing	
  calcium	
  ,	
  alumina	
  and	
  sulphate	
  together	
  to	
  obtain;	
  
ettringite	
  =	
  C4A3Š	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  	
  3CaAl2O3	
  Ÿ	
  3CaSO4	
  Ÿ	
  32H2O	
  	
  
The	
  effect	
  on	
  the	
  binder;	
  
•  rapid	
  set	
  
•  high	
  early	
  strength	
  
•  shrinkage	
  compensation	
  
•  fast	
  drying	
  
•  low	
  alkali	
  
•  no	
  effluoresence	
  
•  improved	
  sulphate	
  resistance	
  
what	
  is	
  needed	
  to	
  form	
  C4A3Š	
  ?	
  
what	
  is	
  needed	
  to	
  form	
  C4A3Š	
  ?	
  
	
  
•  aluminium	
  	
  
•  sulphate	
  
•  calcium	
  	
  
Calumex	
  
Anhydrite,	
  hemi-­‐hydrate,	
  gypsum	
  
Portlandcement,	
  	
  
calcium-­‐oxide/-­‐hydroxide	
  
a	
  fibrous	
  needle	
  shaped	
  crystal	
  ,	
  holding	
  32	
  water	
  molecules	
  
what	
  is	
  to	
  be	
  considered	
  ?	
  
PORTLANDCEMENT	
  
	
  
Content	
  of	
  	
  
	
  
•  C3A	
   	
  tri-­‐calcium	
  aluminate	
  
•  amount	
  of	
  free	
  lime	
  (	
  fCaO	
  )	
  
•  type	
  and	
  amount	
  of	
  sulphate	
  added	
  
CALCIUM	
  SULPHATE	
  
	
  
•  hemi-­‐hydrate	
  
•  micronized	
  gypsum	
  
•  anhydrite	
  
choice	
  of	
  type	
  of	
  CALUMEX	
  
CALCIUM	
  SULPHO	
  ALUMINATE	
  CEMENT	
  
	
  
Content	
  of	
  	
  
	
  
•  CALUMEX	
  CSA	
  –	
  ground	
  clinker	
  ;	
  
•  Al2O3	
  content	
   	
  ~	
  46	
  %	
  
•  SiO2 	
   	
  ~	
  3	
  	
  	
  	
  %	
  
•  fCaO 	
   	
  0 	
  	
  
•  CaSO4 	
   	
  ~	
  7,5	
  %	
  
•  CALUMEX	
  Quick	
  	
  
•  Al2O3	
  content 	
  ~	
  32	
  %	
  
•  SiO2 	
   	
  ~	
  3	
  	
  	
  %	
  
•  fCaO 	
   	
  0	
  
•  CaSO4 	
   	
  ~	
  20	
  % 	
  
	
  	
  	
  
•  BELICEM	
  
•  Al2O3	
  content 	
  ~	
  32	
  %	
  
•  SiO2 	
   	
  ~	
  10	
  	
  %	
  
•  fCaO 	
   	
  0	
  
•  CaSO4 	
   	
  ~	
  10	
  % 	
  
	
  	
  	
  
why	
  is	
  sulphate	
  added	
  to	
  OPC	
  ?	
  
Portlandcement	
  	
  mainly	
  	
  forms	
  minerals;	
  
	
  
•  C3S	
  –	
  alite	
  	
  
•  C2S	
  –	
  belite	
   	
   	
  	
  
•  C3A	
  –	
  tri-­‐calcium	
  aluminate	
  
C3A	
  is	
  the	
  most	
  reactive	
  phase	
  –	
  it	
  forms	
  with	
  water	
  rapidly	
  C4AH	
  
crystals	
  at	
  the	
  surface	
  of	
  C3S	
  –	
  causing	
  rapid	
  setting	
  of	
  the	
  cement	
  
	
  
To	
  retard	
  the	
  quick	
  setting	
  gypsum	
  or	
  anhydrite	
  or	
  a	
  combination	
  of	
  both	
  
is	
  added	
  at	
  the	
  grinding	
  stage	
  of	
  the	
  cement	
  clinker.	
  
	
  
As	
  this	
  generates	
  heat	
  sometimes	
  part	
  of	
  the	
  gypsum	
  is	
  converted	
  to	
  
hemi-­‐hydrate.	
  
	
  
The	
  sulphate	
  reacts	
  with	
  the	
  alumina	
  and	
  enrobes	
  a	
  layer	
  of	
  ettringite	
  
around	
  the	
  C3A	
  particles.	
  
	
  
Thus	
  preventing	
  them	
  to	
  go	
  in	
  solution	
  quickly.	
  
binary	
  system	
  CSA+OPC	
  
	
  	
  
When	
  CSA	
  cement	
  is	
  used	
  most	
  of	
  the	
  sulphate	
  of	
  the	
  OPC	
  is	
  absorbed	
  
immediately	
  by	
  the	
  additional	
  aluminates.	
  
	
  
It	
  therefor	
  cannot	
  act	
  as	
  a	
  retarder	
  of	
  the	
  C3A	
  phase	
  leading	
  to	
  rapid	
  setting	
  of	
  
the	
  matrix.	
  
	
  
The	
  strength	
  development	
  however	
  is	
  limited	
  because	
  still	
  the	
  amount	
  	
  
ettringite	
  is	
  relatively	
  low.	
  
	
  
Also	
  the	
  long	
  term	
  strength	
  is	
  reduced	
  because	
  C3A	
  is	
  putting	
  a	
  gel	
  around	
  the	
  
C3S	
  and	
  C2S	
  phases	
  preventing	
  a	
  regular	
  hydration.	
  
	
  
binary	
  system	
  CSA+OPC	
  
	
  	
  
CSA	
  is	
  more	
  soluble	
  than	
  anhydrite	
  but	
  less	
  soluble	
  than	
  gypsum	
  and	
  hemi-­‐
hydrate.	
  
	
  
So	
  when	
  Calumex	
  is	
  mixed	
  with	
  an	
  OPC	
  that	
  contains	
  anhydrite	
  –	
  Calumex	
  will	
  
dissolute	
  quickly	
  enough	
  to	
  react	
  with	
  the	
  sulphate	
  ions	
  released	
  by	
  anhydrite	
  
thus	
  preventing	
  them	
  to	
  retard	
  the	
  C3A	
  phase	
  of	
  the	
  OPC,	
  giving	
  rapid	
  set	
  at	
  
relative	
  low	
  dosage.	
  
	
  
When	
  on	
  the	
  other	
  hand	
  an	
  OPC	
  is	
  used	
  containing	
  hemi-­‐hydrate	
  –	
  the	
  
dissolution	
  is	
  higher,	
  	
  sulphate	
  ions	
  are	
  released	
  more	
  quickly	
  and	
  react	
  with	
  the	
  
C3A.	
  
	
  
In	
  this	
  case	
  a	
  higher	
  dosage	
  is	
  needed	
  to	
  give	
  the	
  same	
  acceleration.	
  
	
  
binary	
  system	
  CSA+OPC	
  
	
  	
  
In	
  any	
  case	
  if	
  an	
  OPC	
  is	
  used	
  with	
  a	
  higher	
  C3A	
  content	
  it	
  will	
  contribute	
  to	
  a	
  
rapid	
  set.	
  
	
  
A	
  higher	
  free	
  lime	
  content	
  of	
  the	
  OPC	
  –	
  and/or	
  an	
  addition	
  of	
  calcium	
  ions	
  
(calcium	
  oxide/hydroxide)	
  	
  will	
  accelerate	
  the	
  formation	
  of	
  ettringite.	
  
	
  
It	
  is	
  essential	
  to	
  choose	
  the	
  right	
  OPC	
  for	
  the	
  intent	
  use	
  of	
  the	
  mortar	
  	
  
	
  
In	
  any	
  case	
  a	
  stable	
  cement	
  is	
  essential	
  –	
  any	
  variation	
  in	
  free	
  lime	
  content	
  and	
  
amount	
  and	
  type	
  of	
  calcium	
  sulphate	
  (di-­‐hydrated)	
  asks	
  for	
  re-­‐establishing	
  the	
  
amount	
  of	
  CSA	
  to	
  be	
  used.	
  
ternary	
  system	
  CSA+OPC+additional	
  CŠ	
  
	
  	
  
When	
  additional	
  calcium	
  sulphate	
  is	
  added	
  to	
  a	
  blend	
  of	
  CSA	
  and	
  OPC	
  	
  
more	
  ettringite	
  crystals	
  are	
  formed	
  i.e.	
  a	
  higher	
  initial	
  strength	
  is	
  obtained.	
  
	
  
Ettringite	
  is	
  the	
  first	
  	
  strength	
  found	
  	
  
	
  
CALUMEX	
  CSA	
  generally	
  releases	
  more	
  quickly	
  its	
  alumina	
  ions	
  compared	
  to	
  
other	
  sources	
  of	
  calcium	
  aluminate.	
  
	
  
Slow	
  soluble	
  anhydrite	
  is	
  by	
  far	
  the	
  preferred	
  source	
  of	
  sulphate	
  in	
  a	
  Calumex	
  
system	
  –	
  aluminate	
  phases	
  go	
  in	
  solution	
  first	
  allowing	
  to	
  absorb	
  all	
  of	
  the	
  
sulphate	
  (even	
  if	
  the	
  OPC	
  brings	
  hemi-­‐hydrate)	
  and	
  converts	
  it	
  into	
  ettringite	
  
crystals.	
  
	
  
ternary	
  system	
  CSA+OPC+additional	
  CŠ	
  
	
  	
  
Calumex	
  gives	
  no	
  lime	
  nor	
  reactive	
  silicates	
  which	
  guarantees	
  long	
  storage.	
  
The	
  lime	
  needed	
  to	
  form	
  ettringite	
  is	
  taken	
  from	
  the	
  Portlandcement.	
  
	
  
As	
  lime	
  is	
  taken	
  out	
  of	
  the	
  equation	
  –	
  normally	
  acting	
  as	
  a	
  gel	
  preventing	
  silicate	
  
and	
  aluminate	
  phases	
  to	
  go	
  in	
  solution	
  –	
  this	
  further	
  contribute	
  to	
  the	
  increase	
  
of	
  the	
  strength.	
  
	
  
In	
  case	
  more	
  soluble	
  types	
  of	
  calcium	
  sulphate	
  are	
  being	
  used	
  (i.e.	
  hemi-­‐hydrate	
  
–α	
  or	
  β	
  or	
  gypsum)	
  because	
  of	
  their	
  higher	
  solubility	
  –	
  they	
  will	
  react	
  only	
  with	
  
the	
  aluminate	
  phases.	
  
	
  
It	
  will	
  give	
  acceleration	
  of	
  the	
  set	
  –	
  by	
  early	
  formation	
  of	
  ettringite	
  –	
  but	
  to	
  a	
  
lesser	
  extend	
  compared	
  to	
  anhydrite	
  
	
  
The	
  higher	
  solubility	
  leads	
  to	
  slower	
  reaction	
  because	
  it	
  will	
  prevent	
  the	
  C3A	
  to	
  
react.	
  
ternary	
  system	
  CSA+OPC+additional	
  CŠ	
  
	
  	
  
	
  
	
  
To	
  overcome	
  this	
  effect	
  a	
  higher	
  dosage	
  of	
  CSA	
  is	
  needed	
  	
  
	
  
An	
  ideal	
  binder	
  system	
  combining	
  all	
  elements	
  of	
  rapid	
  set,	
  high	
  early	
  strength	
  
and	
  shrinkage	
  compensation	
  could	
  be	
  2	
  parts	
  of	
  OPC	
  CEM	
  I	
  42,5R	
  to	
  1	
  part	
  of	
  
Calumex	
  Quick.	
  
binary	
  system	
  ACA+CŠ	
  
	
  	
  
An	
  ideal	
  binder	
  system	
  is	
  a	
  combination	
  of	
  amorphous	
  calcium	
  aluminate	
  and	
  
calcium	
  sulphate	
  –	
  without	
  addition	
  of	
  OPC.	
  
	
  
As	
  the	
  CaO	
  to	
  Al2O3	
  ratio	
  is	
  to	
  the	
  advantage	
  of	
  calcium	
  and	
  the	
  main	
  phase	
  
formed	
  by	
  the	
  alumina	
  phase	
  is	
  C12A7	
  –	
  the	
  reaction	
  with	
  sulphate	
  is	
  much	
  faster	
  
and	
  more	
  C4A3Š	
  is	
  formed	
  without	
  the	
  further	
  addition	
  of	
  lime	
  (i.e.	
  OPC)	
  
	
  
The	
  reaction	
  in	
  short	
  is	
  ;	
  
	
  
	
   	
   	
  C12A7+3CŠ 	
  C4A3Š	
  +	
  AH3 	
  	
  
	
  
	
  
When	
  used	
  as	
  an	
  addition	
  to	
  Portlandcement	
  the	
  excess	
  of	
  lime	
  will	
  give	
  an	
  
instant	
  setting	
  of	
  the	
  binder	
  ,	
  and	
  the	
  high	
  amount	
  of	
  ettringite	
  formed	
  gives	
  an	
  
extreme	
  fast	
  strength	
  development.	
  
	
  
There	
  is	
  no	
  risk	
  on	
  “conversion”	
  of	
  the	
  hydrates	
  in	
  time.	
  
	
  
conclusion	
  
CALTRA	
  offers	
  a	
  wide	
  range	
  of	
  calcium	
  aluminate	
  ,	
  calcium	
  sulpho	
  aluminate	
  and	
  
amorphous	
  calcium	
  aluminates	
  giving	
  formulators	
  the	
  complete	
  freedom	
  to	
  
choose	
  the	
  correct	
  type	
  to	
  satisfy	
  their	
  needs.	
  
	
  
CALTRA	
  continues	
  to	
  develop	
  binders	
  and	
  binder	
  systems	
  for	
  specific	
  
applications.	
  
	
  
Some	
  of	
  the	
  latest	
  ;	
  
	
  
CALUMEX	
  WHITE	
  –	
  a	
  white	
  CSA	
  for	
  decorative	
  screeds	
  ,	
  terrazzo	
  ,	
  decorative	
  
prefab	
  concrete	
  –	
  GRC	
  panels	
  ,	
  tile	
  grouts	
  –	
  natural	
  stone	
  adhesives	
  etc.	
  
	
  
CEM-­‐FLUX	
  –	
  a	
  cement	
  designed	
  for	
  the	
  RMC	
  plants	
  as	
  a	
  ready	
  binder	
  for	
  
pumpable	
  screeds	
  
	
  
ULTRA-­‐FLUX	
  –	
  a	
  cement	
  for	
  decorative	
  overlayments	
  	
  
R&D	
  
CALTRA	
  has	
  its	
  own	
  r&d	
  lab	
  –	
  ready	
  to	
  answer	
  any	
  queries	
  you	
  may	
  have.	
  
	
  
To	
  further	
  improve	
  or	
  optimize	
  existing	
  	
  products	
  or	
  help	
  develop	
  new	
  
products.	
  
	
  
	
  
We	
  work	
  closely	
  together	
  with	
  our	
  customers	
  in	
  strict	
  confidentiality	
  –	
  to	
  
mutual	
  benefit.	
  
	
  

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CEMENT in Ternary system

  • 2. So  called  ternary  systems  are  being  used  for  several  decades  by  the  construction   chemistry  predominantly  in  making  self-­‐leveling  screeds  ,  under-­‐  and  over   layments  –  non  shrink  grouts  ,  repair  mortars  etc.   They  are  based  on  mixing  calcium  ,  alumina  and  sulphate  together  to  obtain;   ettringite  =  C4A3Š                                  3CaAl2O3  Ÿ  3CaSO4  Ÿ  32H2O     The  effect  on  the  binder;   •  rapid  set   •  high  early  strength   •  shrinkage  compensation   •  fast  drying   •  low  alkali   •  no  effluoresence   •  improved  sulphate  resistance   what  is  needed  to  form  C4A3Š  ?  
  • 3. what  is  needed  to  form  C4A3Š  ?     •  aluminium     •  sulphate   •  calcium     Calumex   Anhydrite,  hemi-­‐hydrate,  gypsum   Portlandcement,     calcium-­‐oxide/-­‐hydroxide   a  fibrous  needle  shaped  crystal  ,  holding  32  water  molecules  
  • 4. what  is  to  be  considered  ?   PORTLANDCEMENT     Content  of       •  C3A    tri-­‐calcium  aluminate   •  amount  of  free  lime  (  fCaO  )   •  type  and  amount  of  sulphate  added   CALCIUM  SULPHATE     •  hemi-­‐hydrate   •  micronized  gypsum   •  anhydrite  
  • 5. choice  of  type  of  CALUMEX   CALCIUM  SULPHO  ALUMINATE  CEMENT     Content  of       •  CALUMEX  CSA  –  ground  clinker  ;   •  Al2O3  content    ~  46  %   •  SiO2    ~  3        %   •  fCaO    0     •  CaSO4    ~  7,5  %   •  CALUMEX  Quick     •  Al2O3  content  ~  32  %   •  SiO2    ~  3      %   •  fCaO    0   •  CaSO4    ~  20  %         •  BELICEM   •  Al2O3  content  ~  32  %   •  SiO2    ~  10    %   •  fCaO    0   •  CaSO4    ~  10  %        
  • 6. why  is  sulphate  added  to  OPC  ?   Portlandcement    mainly    forms  minerals;     •  C3S  –  alite     •  C2S  –  belite         •  C3A  –  tri-­‐calcium  aluminate   C3A  is  the  most  reactive  phase  –  it  forms  with  water  rapidly  C4AH   crystals  at  the  surface  of  C3S  –  causing  rapid  setting  of  the  cement     To  retard  the  quick  setting  gypsum  or  anhydrite  or  a  combination  of  both   is  added  at  the  grinding  stage  of  the  cement  clinker.     As  this  generates  heat  sometimes  part  of  the  gypsum  is  converted  to   hemi-­‐hydrate.     The  sulphate  reacts  with  the  alumina  and  enrobes  a  layer  of  ettringite   around  the  C3A  particles.     Thus  preventing  them  to  go  in  solution  quickly.  
  • 7. binary  system  CSA+OPC       When  CSA  cement  is  used  most  of  the  sulphate  of  the  OPC  is  absorbed   immediately  by  the  additional  aluminates.     It  therefor  cannot  act  as  a  retarder  of  the  C3A  phase  leading  to  rapid  setting  of   the  matrix.     The  strength  development  however  is  limited  because  still  the  amount     ettringite  is  relatively  low.     Also  the  long  term  strength  is  reduced  because  C3A  is  putting  a  gel  around  the   C3S  and  C2S  phases  preventing  a  regular  hydration.    
  • 8. binary  system  CSA+OPC       CSA  is  more  soluble  than  anhydrite  but  less  soluble  than  gypsum  and  hemi-­‐ hydrate.     So  when  Calumex  is  mixed  with  an  OPC  that  contains  anhydrite  –  Calumex  will   dissolute  quickly  enough  to  react  with  the  sulphate  ions  released  by  anhydrite   thus  preventing  them  to  retard  the  C3A  phase  of  the  OPC,  giving  rapid  set  at   relative  low  dosage.     When  on  the  other  hand  an  OPC  is  used  containing  hemi-­‐hydrate  –  the   dissolution  is  higher,    sulphate  ions  are  released  more  quickly  and  react  with  the   C3A.     In  this  case  a  higher  dosage  is  needed  to  give  the  same  acceleration.    
  • 9. binary  system  CSA+OPC       In  any  case  if  an  OPC  is  used  with  a  higher  C3A  content  it  will  contribute  to  a   rapid  set.     A  higher  free  lime  content  of  the  OPC  –  and/or  an  addition  of  calcium  ions   (calcium  oxide/hydroxide)    will  accelerate  the  formation  of  ettringite.     It  is  essential  to  choose  the  right  OPC  for  the  intent  use  of  the  mortar       In  any  case  a  stable  cement  is  essential  –  any  variation  in  free  lime  content  and   amount  and  type  of  calcium  sulphate  (di-­‐hydrated)  asks  for  re-­‐establishing  the   amount  of  CSA  to  be  used.  
  • 10. ternary  system  CSA+OPC+additional  CŠ       When  additional  calcium  sulphate  is  added  to  a  blend  of  CSA  and  OPC     more  ettringite  crystals  are  formed  i.e.  a  higher  initial  strength  is  obtained.     Ettringite  is  the  first    strength  found       CALUMEX  CSA  generally  releases  more  quickly  its  alumina  ions  compared  to   other  sources  of  calcium  aluminate.     Slow  soluble  anhydrite  is  by  far  the  preferred  source  of  sulphate  in  a  Calumex   system  –  aluminate  phases  go  in  solution  first  allowing  to  absorb  all  of  the   sulphate  (even  if  the  OPC  brings  hemi-­‐hydrate)  and  converts  it  into  ettringite   crystals.    
  • 11. ternary  system  CSA+OPC+additional  CŠ       Calumex  gives  no  lime  nor  reactive  silicates  which  guarantees  long  storage.   The  lime  needed  to  form  ettringite  is  taken  from  the  Portlandcement.     As  lime  is  taken  out  of  the  equation  –  normally  acting  as  a  gel  preventing  silicate   and  aluminate  phases  to  go  in  solution  –  this  further  contribute  to  the  increase   of  the  strength.     In  case  more  soluble  types  of  calcium  sulphate  are  being  used  (i.e.  hemi-­‐hydrate   –α  or  β  or  gypsum)  because  of  their  higher  solubility  –  they  will  react  only  with   the  aluminate  phases.     It  will  give  acceleration  of  the  set  –  by  early  formation  of  ettringite  –  but  to  a   lesser  extend  compared  to  anhydrite     The  higher  solubility  leads  to  slower  reaction  because  it  will  prevent  the  C3A  to   react.  
  • 12. ternary  system  CSA+OPC+additional  CŠ           To  overcome  this  effect  a  higher  dosage  of  CSA  is  needed       An  ideal  binder  system  combining  all  elements  of  rapid  set,  high  early  strength   and  shrinkage  compensation  could  be  2  parts  of  OPC  CEM  I  42,5R  to  1  part  of   Calumex  Quick.  
  • 13. binary  system  ACA+CŠ       An  ideal  binder  system  is  a  combination  of  amorphous  calcium  aluminate  and   calcium  sulphate  –  without  addition  of  OPC.     As  the  CaO  to  Al2O3  ratio  is  to  the  advantage  of  calcium  and  the  main  phase   formed  by  the  alumina  phase  is  C12A7  –  the  reaction  with  sulphate  is  much  faster   and  more  C4A3Š  is  formed  without  the  further  addition  of  lime  (i.e.  OPC)     The  reaction  in  short  is  ;          C12A7+3CŠ  C4A3Š  +  AH3         When  used  as  an  addition  to  Portlandcement  the  excess  of  lime  will  give  an   instant  setting  of  the  binder  ,  and  the  high  amount  of  ettringite  formed  gives  an   extreme  fast  strength  development.     There  is  no  risk  on  “conversion”  of  the  hydrates  in  time.    
  • 14. conclusion   CALTRA  offers  a  wide  range  of  calcium  aluminate  ,  calcium  sulpho  aluminate  and   amorphous  calcium  aluminates  giving  formulators  the  complete  freedom  to   choose  the  correct  type  to  satisfy  their  needs.     CALTRA  continues  to  develop  binders  and  binder  systems  for  specific   applications.     Some  of  the  latest  ;     CALUMEX  WHITE  –  a  white  CSA  for  decorative  screeds  ,  terrazzo  ,  decorative   prefab  concrete  –  GRC  panels  ,  tile  grouts  –  natural  stone  adhesives  etc.     CEM-­‐FLUX  –  a  cement  designed  for  the  RMC  plants  as  a  ready  binder  for   pumpable  screeds     ULTRA-­‐FLUX  –  a  cement  for  decorative  overlayments    
  • 15. R&D   CALTRA  has  its  own  r&d  lab  –  ready  to  answer  any  queries  you  may  have.     To  further  improve  or  optimize  existing    products  or  help  develop  new   products.       We  work  closely  together  with  our  customers  in  strict  confidentiality  –  to   mutual  benefit.