A  Reaction-­Diffusion  Model  to  Determine  Mesoscale  Patterns  

in  Cement  Paste  
Research  Brief,  Issue  7,  Volume  2018    

 
PROBLEM   Low µSlow
Fast chemical diffusion res chemical diffusion High µres <latexit sha1_base64="0AE5qkCELIth/ZgTInCZsMHwX9s=">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</latexit> <latexit sha1_base64="sVM4rTg7M/Gn1LlvKutBI5vp49Y=">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</latexit>
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Strength  and  toughness,  two  important  aspects  of  the   of C-S-H grains of C-S-H grains
durability  of  concrete  structures,  are  dramatically  influenced  by  
the  material’s  nanotexture,  but  the  question  of  how  the  building  

˜ = 0.2
blocks  of  cement  paste  organize  themselves  to  create  this  

advancing cement hydration

nanotexture  is  still  being  answered.  
 

<latexit sha1_base64="QsoN7sn6bwbRSDhaqj0g9Rgxtyk=">AAACPXicbVDLSsNAFJ34rPXVVnduBovgKiRFUBdC0Y3LCsYW2lAmk0k7dCYJMzfSEvorbvUz/A1/wJW4dev0sbCtBwYO557LPXOCVHANjvNhra1vbG5tF3aKu3v7B4elcuVJJ5mizKOJSFQrIJoJHjMPOAjWShUjMhCsGQzuJvPmM1OaJ/EjjFLmS9KLecQpASN1S5UOcBGyvNPo8zG+wY5d65aqju1MgVeJOydVNEejW7aOO2FCM8lioIJo3XadFPycKOBUsHGxk2mWEjogPdY2NCaSaT+fhh/jM6OEOEqUeTHgqfp3IydS65EMjFMS6Ovl2UT8d6ZBEjVS4cL9fOJTOtKLasSHAoa15awQXfk5j9MMWExnUaNMYEjwpEsccsUoiJEhhCpufotpnyhCwTReND26y62tEq9mX9vuw0W1fjsvtIBO0Ck6Ry66RHV0jxrIQxQN0Qt6RW/Wu/VpfVnfM+uaNd85Qguwfn4BKD+uLw==</latexit>
Recent  modelling  efforts  by  CSHub  researchers  demonstrated  
1

˜ = 0.5
a  convincing  pathway.  Upon  mixing  water  with  cement  clinker,  
ions  dissolve  into  the  pore  solution  and  precipitate  out  
nanometer-­sized  grains  of  calcium-­silicate-­hydrates  (C-­S-­H).  

<latexit sha1_base64="IUZGZJJZVux/Sy6NyskbpzIqqRU=">AAACPXicbVDLSsNAFJ3UV62vtrpzM1gEVyUpiroQim5cVjC20JQymUzaoZMHMzfSEvorbvUz/A1/wJW4deukzcK2Hhg4nHsu98xxY8EVmOaHUVhb39jcKm6Xdnb39g/KleqTihJJmU0jEcmOSxQTPGQ2cBCsE0tGAlewtju6y+btZyYVj8JHmMSsF5BByH1OCWipX646wIXHUqc15FN8g836Rb9cM+vmDHiVWDmpoRytfsU4cryIJgELgQqiVNcyY+ilRAKngk1LTqJYTOiIDFhX05AETPXSWfgpPtWKh/1I6hcCnql/N1ISKDUJXO0MCAzV8iwT/50pCIicSG/hfpr5pPLVourzsYBxYzkr+Fe9lIdxAiyk86h+IjBEOOsSe1wyCmKiCaGS699iOiSSUNCNl3SP1nJrq8Ru1K/r1sN5rXmbF1pEx+gEnSELXaImukctZCOKxugFvaI34934NL6M77m1YOQ7h2gBxs8vLZGuMg==</latexit>
These  building  blocks  are  the  glue  that  binds  sand  and  gravel   µlow
res µhigh
res

together  and  the  primary  ingredient  for  concrete.  The  

40 Da = 1 Da = 1
Da = 10 Da = 10

0.8
organization  of  these  C-­S-­H  grains  drastically  influences   Da = 100 Da = 100

˜ =s̃sp
concrete’s  mechanical  performance.  By  better  understanding   20
which  parameters  influence  this  organization,  we  hope  to  

<latexit sha1_base64="wU5Qc9LfuQ8cG1j9XmZ61lbN5F0=">AAACPXicbVDLSsNAFJ3UV62vtrpzM1gEVyUpgnUhFN24rGBtoQllMpm0QycPZm6kJfRX3Opn+Bv+gCtx69ZJm4VtPTBwOPdc7pnjxoIrMM0Po7CxubW9U9wt7e0fHB6VK9UnFSWSsg6NRCR7LlFM8JB1gINgvVgyEriCdd3xXTbvPjOpeBQ+wjRmTkCGIfc5JaClQblqAxceS+32iM/wDTbrzUG5ZtbNOfA6sXJSQznag4pxYnsRTQIWAhVEqb5lxuCkRAKngs1KdqJYTOiYDFlf05AETDnpPPwMn2vFw34k9QsBz9W/GykJlJoGrnYGBEZqdZaJ/84UBEROpbd0P818UvlqWfX5RMCksZoV/KaT8jBOgIV0EdVPBIYIZ11ij0tGQUw1IVRy/VtMR0QSCrrxku7RWm1tnXQa9eu69XBZa93mhRbRKTpDF8hCV6iF7lEbdRBFE/SCXtGb8W58Gl/G98JaMPKdY7QE4+cXMuOuNQ==</latexit>
create  longer-­lasting,  more  durable  materials.   0
(b)
101
APPROACH    

m̃z
mean pore size
We  applied  a  new  technique  to  model  the  reaction  rate  and   100
chemical  diffusion  of  the  C-­S-­H  grains  during  the  early  stages   0 1 2 3 4 5
m̃z

t̃
of  cement  setting.  Rather  than  track  the  formation  and  
1
interaction  of  the  discrete  nanograins  explicitly,  the  model   10
predicts  how  the  spatial  distribution  and  packing  density  of  the  
mobile kinetically arrestest
C-­S-­H  grains  change  over  time.  As  an  example,  Figure  1  to  the   2
right  displays  the  evolution  of  these  density  patterns  for  several   10
0.25 ˜p 0.50 0.75 1.00
reaction  environments  that  correspond  to  increasing  degrees   ˜
of  supersaturation.  Both  the  local  packing  density  of  C-­S-­H  and   mean packing fraction
its  connectivity  determine  the  overall  strength  and  toughness  
Figure  1:  (Top)  Cement  patterns  developing  under  
of  cement.  
differing  reaction  environments.  Slower,  more  
heterogeneous  reaction  rates  create  more  distinct  phase  
FINDINGS     separation,  causing  larger  pores  to  form.  (Bottom)  Mean  
pore  size  plotted  against  the  overall  reaction  extent  
We  find  that  the  speed  and  uniformity  at  which  the  C-­S-­H  
(inset-­  plotted  against  normalized  time);;  line  colors  
grains  precipitate  from  solution  determines  the  size  and   indicate  how  rapidly  C-­S-­H  grains  diffuse  during  the  initial  
contrast  of  the  density  patterns.  For  the  same  hydration   period  of  nucleus  formation  (blue  -­  fast  diffusion,  green  –  
degree,  Fig.  1  shows  that  homogenous  reaction  rates,  which   slow  diffusion),  and  solid  (dashed)  lines  indicate  systems  
have  little  chemical  diffusion,  produce  systems  with  smaller   of  low  (high)  supersaturation.    
capillary  pores  and  more  loosely  packed  grains.  More  dramatic  
phase  separation  is  found  in  heterogeneously  precipitating  
systems,  which  have  substantial  chemical  diffusion;;  here,  C-­ WHY  DOES  THIS  RESEARCH  MATTER?  
S-­H  grains  pack  together  and  form  nuclei  more  readily.    
Importantly,  these  results  demonstrate  that  the  interaction  of   • If  the  reaction  environment  and  interaction  
the  grains  during  the  initial  few  hours  of  the  cement  reaction   of  C-­S-­H  grains  during  the  early  stages  of  
control  the  uniformity  of  the  patterns  that  form  and  provide  a   cement  setting  can  be  controlled,  a  tougher  
template  upon  which  C-­S-­H  grains  continue  to  precipitate  at   more  resilient  material  may  be  engineered  
later  stages  of  the  reaction.   by  modifying  its  nanotexture.  

                                                                                                               
1
 Ioannidou,  Katerina,  et  al.  "Mesoscale  texture  of  cement  hydrates."  Proceedings  of  the  National  Academy  of  Sciences  (2016)  

This  research  was  carried  out  by  the  CSHub@MIT  with  sponsorship  provided  by  the  Portland  Cement  Association  and  the  Ready  Mixed  
Concrete  Research  &  Education  Foundation.  CSHub@MIT  is  solely  responsible  for  content.  Authors:  Thomas  Petersen,  Martin  Z.  Bazant,  
Roland  J.-­M.  Pellenq,  Franz-­Josef  Ulm.