Cement Hydration

[rockson.aluah@und.edu]

Hi Everyone,
Please, I am reaching out to request assistance in obtaining the thermodynamic database for the following cement-formulated minerals, as they are not available in the standard PHREEQC database:  Alite   (Ca3SiO5), Brownmillerite   Ca₂(Fe,Al)O₅), Pavlovskyite [Ca₈Si₅O₁₈)],
C-S-H [Ca3Si2O7?3H2O], Dicalcium Silicate   [Ca₂SiO₄], Larnite [Ca₂SiO₄],
Clinoenstatite [MgSiO3] and  Xonotlite [Ca6Si6O17(OH)2].
If anyone has access to this data or knows of a suitable source, I would greatly appreciate your help.

Thank you in advance for your support!

[dlparkhurst]

There are databases specializing in cement minerals that are distributed with PHREEQC:
Concrete_PHR.dat
Concreter_PZ.dat

Here are names of some other databases that you may be able to track down:
CEMDATA URL: https://www.empa.ch/web/s308/thermodynamic-data
CEMDATA18-31-03-2022-phaseVol.dat    PKDLM_BRGM_database_phreeqc_ThermoddemV1.10_06Jun2017.dat
CEMDATA18.1-16-01-2019-phaseVol.dat  PSINA_12_07_110615_DAV_s_win.dat
CEMDATA18.dat                       
IU-bl-2kb.dat
ThermoChimie_PhreeqC_SIT_electron_v10a.dat
Thermochimie_PhreeqC_eDH_oxygen_v10a.dat
ThermoddemV1.10_15Dec2020.dat


Ca3SiO5 in PHREEQC databases:

Code: [Select]

Kinec.v2.dat:   Ca3SiO5 + 6 H+ = SiO2 + 3 Ca+2 + 3 H2O
Kinec_v3.dat:   Ca3SiO5 + 6 H+ = SiO2 + 3 Ca+2 + 3 H2O
core10.dat:     Ca3SiO5 + 6 H+ = SiO2 + 3 Ca+2 + 3 H2O
core11_idealgas.dat:    Ca3SiO5 + 6 H+ = SiO2 + 3 Ca+2 + 3 H2O
llnl.dat:        Ca3SiO5 + 6 H+ = SiO2 + 3 Ca+2 + 3 H2O
minteq.dat:Ca3SiO5
minteq.dat:        Ca3SiO5 + 6 H+ = H4SiO4 + 3 Ca+2 + H2O

Formulas found in other files--------

Ca3Si2O7 is in IU-bl-2kb.dat with the following header information:

Code: [Select]

# Developed by Guanru Zhang, Peng Lu, Yilun Zhang, Kevin Tu, and Chen Zhu
# All inquiries should be directed to supcrt@indiana.edu
# On 4/1/2019
# Citation: Zhang GR, Lu P, Zhang YL, Tu K, Zhu C (in review) SUPPHREEQC: A program
#    to generate customized PHREEQC thermodynamic databases from SUPCRTBL and
#    to extend calculations to elevated pressures and temperatures. Computers &
#    Geosciences
# Visit https://hydrogeochem.earth.indiana.edu for updates

Larnite:
PKDLM_BRGM_database_phreeqc_ThermoddemV1.10_06Jun2017.dat:Larnite(alpha)
PKDLM_BRGM_database_phreeqc_ThermoddemV1.10_06Jun2017.dat:Larnite(beta)
PKDLM_BRGM_database_phreeqc_ThermoddemV1.10_06Jun2017.dat:Larnite(gamma)
ThermoddemV1.10_15Dec2020.dat:Larnite(alpha)
ThermoddemV1.10_15Dec2020.dat:Larnite(beta)
ThermoddemV1.10_15Dec2020.dat:Larnite(gamma)

MgSiO3:
CEMDATA18-31-03-2022-phaseVol.dat:Mg+2 + H2O + SiO2 = MgSiO3 + 2H+
CEMDATA18.1-16-01-2019-phaseVol.dat:Mg+2 + H2O + SiO2 = MgSiO3 + 2H+
CEMDATA18.dat:Mg+2 + H2O + SiO2 = MgSiO3 + 2H+
PKDLM_BRGM_database_phreeqc_ThermoddemV1.10_06Jun2017.dat:MgSiO3 + 2.000H+ + 1.000H2O = 1.000Mg+2 + 1.000H4SiO4
ThermoddemV1.10_15Dec2020.dat:MgSiO3 + 2.000H+ + 1.000H2O = 1.000Mg+2 + 1.000H4SiO4

Ca6Si6O17(OH)2:
PKDLM_BRGM_database_phreeqc_ThermoddemV1.10_06Jun2017.dat:Ca6Si6O17(OH)2 + 12.000H+ + 5.000H2O = 6.000Ca+2 + 6.000H4SiO4
ThermoChimie_PhreeqC_SIT_electron_v10a.dat:Ca6Si6O17(OH)2     = 6.000Ca+2     - 12.000H+     + 6.000H4(SiO4)     - 5.000H2O
Thermochimie_PhreeqC_eDH_oxygen_v10a.dat:Ca6Si6O17(OH)2     = 6.000Ca+2     - 12.000H+     + 6.000H4(SiO4)     - 5.000H2O
ThermoddemV1.10_15Dec2020.dat:Ca6Si6O17(OH)2 + 12.000H+ + 5.000H2O = 6.000Ca+2 + 6.000H4SiO4

[rockson.aluah@und.edu]

Dear Dr. Parkhurst,

Thank you very much for your swift assistance. I was able to locate most of the minerals from the suggested Cement database. However, I am still missing data for two minerals,  Brownmillerite   Ca₂(Fe,Al)O₅) and Pavlovskyite [Ca₈Si₅O₁₈)]

I have been searching for their thermodynamic data without success. Could you kindly assist me in locating a database or source for these two minerals? Your help would be greatly appreciated.

Thank you once again for your support.

Rockson Aluah

[dlparkhurst]

Sorry, that's all I've got.

[rockson.aluah@und.edu]

Hi Dr.  Parkhurst,
I am trying to predict the mineral composition of hydrated cement with respect to temperature and calculate the mole quantities of hydration products at 150C over a 30-day period. Please can you assist me by reviewing my input file, assuming some values, and running it for me? Your help would be greatly appreciated.

Thank you once again for your support.


# Define the brine solution
SOLUTION 1 Brine
    temp      150      # Initial temperature, will change later
    pH        7.0      # Neutral pH
    pe        4.0      # Redox potential
    redox     pe
    units     mg/l
    density   1

   
    K         75400   # Potassium
    Mg        111     # Magnesium
    Ca        3770    # Calcium
    Cl        1950    # Chloride
    S(6)      81982   # Sulfate as S(6)
    Alkalinity 260 as HCO3
    -water    1       # 1 kg of water

# Define cement phases
EQUILIBRIUM_PHASES 1
   
    CSH3T-T2C 0 76.74
    Gypsum    0 746.42
    Portlandite 0 46.73
    C4AF 0 48.64
    C3S 0 48.64

PHASES

Gypsum # from phreeqc.dat
   CaSO4:2H2O = Ca+2 + SO4-2 + 2 H2O
   -log_k -4.58
   -delta_h -0.109 kcal
   -analytic   68.2401   0.0   -3221.51   -25.0627
   -analytical_expression  93.7  5.99E-03  -4e3  -35.019 # better fits the appendix data of Appelo, 2015, AG 55, 62
   -Vm 73.9 # 172.18 / 2.33  (Vm H2O = 13.9 cm3/mol)



CSH3T-T2C # from CEMDATA18.dat
   ((CaO)0.75(SiO2)0.5(H2O)1.25)2 + 3H+ = 1.5Ca+2 + 4H2O + SiO2
   -Vm   80.5584
   -analytic -18.242686 0 7428.082891 7.517428 0 0 0
   -log_K 25.270837




C4AF # from CEMDATA18.dat
      (CaO)4(Al2O3)(Fe2O3) + 4H+ = 2FeO2- + 4Ca+2 + 2AlO2- + 2H2O
   -Vm   130.202
   -analytic   307.746518 0 6436.091359 -112.699532 0 0 0
   -log_K   50.893809 



Portlandite # from CEMDATA18.dat 
   Ca(OH)2 + 2H+ = Ca+2 + 2H2O
   -Vm   33.06
   -analytic -11.299363 0 7301.394065 3.883957 0 0 0
   -log_K 22.799937    


C3S # from CEMDATA18.dat
     (CaO)3SiO2 + 6H+ = 3Ca+2 + 3H2O + SiO2
   -Vm   73.18
   -analytic -6.720801 0 23294.175088 0.748984 0 0 0
   -log_K   73.405906





REACTION_TEMPERATURE 1
    150 150 150 150

REACTION 1
30 in 30 steps


SELECTED_OUTPUT
    -file ALUAH_cement03.xls
    -temperature true
    -pH true
    -alkalinity true
    -totals Ca Mg K Cl S(6) Alkalinity
    -si Gypsum CSH3T-T2C Portlandite C4AF C3S
    -equilibrium_phases  CSH3T-T2C   Gypsum   Portlandite  C4AF  C3S
# Run simulation

[dlparkhurst]

Sorry, I tend not to review scripts. You are the one that knows what you want the script to do, not me. I will answer specific questions about how PHREEQC operates.

[rockson.aluah@und.edu]

Dear Dr. Parkhurst,

Thank you for your prompt response. sorry for the disturbance.

I have used PHREEQC to model cement hydration to evaluate the effect of temperature on cement mineral composition and the number of moles over a 30-day period. However, I am not observing the expected effects in the output file.

Could you kindly provide guidance on this?

Thank you for your time and assistance.

[dlparkhurst]

I do not know what you expected.

[rockson.aluah@und.edu]

Dear Dr. Parkhurst,

Thank you for your prompt response. There is no reaction on the cement mineral composition and the moles are not showing in the output file.
Thanks

[dlparkhurst]

You have not defined  a chemical formula for the REACTION, so nothing is added to the solution by the REACTION definition.

Code: [Select]

REACTION 1
30 in 30 steps
END

Otherwise, you have defined  EQUILIBRIUM_PHASES, so the solution composition will be in equilibrium with the same set of minerals at each reaction step, so there will be no change in solution composition.

If you add a REACTION or change temperature, then the solution composition will change.