Transport in Concrete (1)

David Trejo and O. Burkan Isgor

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 1

Transport phenomena
and durability
• Why is transport phenomena in concrete important?
• Transport of what?
– Heat
– Moisture
– Ions (e.g. Cl-, OH-, SO42-, etc.)
– Gasses (e.g. O2, CO2)

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 2

How do ions move?
• Diffusion
– Ions move (in water) due to a concentration gradient
• Movement of ions with moving water
– Ions move (with water) that is under hydraulic pressure gradient
– Ions move (with water) due to moisture gradient
• (Electrical) Migration
– Ions move due to electrical potential gradient
• Movement due to ionic interactions
– Ions move due to interactions with other ions (activity)

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 3

Ionic diffusion in water

Water is not moving…

“Blausen 0315 Diffusion” by BruceBlaus

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 4

Ionic movement with in water

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 5

Ionic movement with in water

v = velocity of water

v>0

Question: Why would water move?

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 6
Ionic flux
FLUX VECTOR (N, J, F, etc.):
Amount of substance (e.g. ion) passing through per unit area per unit time

Unit: MASS/AREA-TIME (e.g. mol/m2-s, g/cm2-s, etc.)

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 7

Diffusion flux
Fick’s First Law
∂ci
Ni = − Di (1D)
∂x
∂ci ∂ci (2D)
Ni = − Di − Di
∂x ∂y
∂ci ∂ci ∂ci
Ni = − Di − Di − Di (3D)
∂x ∂y ∂z

Ni =− Di∇ci (1D, 2D, or 3D) ci = Concertation of ion i (e.g. chloride) in solvent (e.g. water)

∂ ∂ ∂ Di = Diffusion coefficient of ion i (e.g. chloride) in solvent (e.g. water)

∇
= + +
∂x ∂y ∂z (also called “the self diffusion coefficient”)

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 8

Diffusion flux

Einstein’s Equation
(Universal gas constant, 8.3143 J/mol-K))

(Temperature, K)
(Mobility of the ion at 25oC)

Example: Ions in water at 25oC

(Valance # of the ion)

(Faraday’s constant, 96,488 C/mol)

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 9

Advective (convective) flux

v = velocity of water (m/s)

Question: Why would water move?
(Or why do we have v?)
v>0
• Pressure head (Darcy’s Law)
v =− K ∇h
(For porous media)
• Capillary suction (negative pressure)
Ni = vci
• Wicking (moisture gradient)

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 10

Advective-diffusion flux

Advective flux: Ni = vci

Diffusion flux: Ni =− Di∇ci
Advective-diffusion flux: Ni = vci − Di∇ci

Advective-diffusion flux (1D in x direction):

v = velocity of water (m/s) ∂ci

=
Ni vxci − Di
∂x

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 11

Flux due to electrical potential
Ions move due to electrical potential gradient

DiziF
Ni =
− ci∇φ
RT
zi: valance electron number for the ion (e.g. for Cl-, z=1)
F: Faraday's constant (96,488 C/mol)
R: Universal gas constant (8.3143 J/mol/K)
T: Temperature (K)
φ: electric potential (V)

Question: What are some examples this might apply?

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 12

Flux due to ionic interactions
Ions move due to interactions with other ions

− Dici∇ ln γ i
Ni = Question: How important is it?

γi: activity of ion i With ionic interactions Without interactions

Karadakis, 2010
OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 13
Total flux ( in water !!! )

Di zi F
Ni=ci 𝒗𝒗 − Di 𝛻𝛻ci − ci 𝛻𝛻𝛻 − Di ci 𝛻𝛻 ln γi
RT

Ionic flux due to electrical

Ionic flux due to water
potential gradient
movement
Ionic flux due to interactions
Ionic flux due to water between ions (chemical activity)
movement

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 14

Total flux ( in water !!! )
In 1D (x direction):

∂ci DiziF ∂φ ∂
Ni =vxci − Di − ci − Dici ln γ i
∂x RT ∂x ∂x

Ionic flux due to water Ionic flux due to electrical

movement potential gradient
Ionic flux due to interactions
Ionic flux due to water between ions (chemical activity)
movement

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 15

Ionic transport in water vs concrete

Question: Can we still use the self

diffusion coefficient of the ion i in water?

Question: Can we assume Di = Di,concrete?

ion i
Question: If not, Di,concrete=?

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 16

Ionic transport in water vs concrete

(Formation factor)

ion i
𝑟𝑟𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
𝐹𝐹 =
𝑟𝑟𝑝𝑝

𝑝𝑝
𝐷𝐷𝑖𝑖, 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑟𝑟𝑝𝑝𝑠𝑠 (Electrical resistivity of pore solution)
=
𝐷𝐷𝑖𝑖 𝑟𝑟𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 (Electrical resistivity of concrete)

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 17

Total flux ( in concrete !!! )

Di,c zi F
Ni=ci 𝒗𝒗 − Di,c 𝛻𝛻ci − ci 𝛻𝛻𝛻 − Di,c ci 𝛻𝛻 ln γi
RT

Ionic flux due to electrical

Ionic flux due to water
potential gradient
movement
Ionic flux due to interactions
Ionic flux due to water between ions (chemical activity)
movement

𝐷𝐷𝑖𝑖
Di,c=𝐷𝐷𝑖𝑖 , 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 =
𝐹𝐹

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 18

Mass conservation equation
∂ci
+ ∇ ⋅ ( Ni ) = 0 (Nernst-Planck Equation)
∂t
(Without chemical reactions)

𝜕𝜕ci Di,c zi F
+ 𝛻𝛻 � (ci v − Di,c 𝛻𝛻ci − Di,c ci 𝛻𝛻 ln γi − ci 𝛻𝛻𝛻) = 0
𝜕𝜕𝜕 RT
(With chemical reactions)

𝜕𝜕ci Di,c zi F 𝜕𝜕ci,r

+ 𝛻𝛻 � ci v − Di,c 𝛻𝛻ci − Di,c ci 𝛻𝛻 ln γi − ci 𝛻𝛻𝛻 + =0
𝜕𝜕𝜕 RT 𝜕𝜕𝜕

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 19

N-P equation
𝜕𝜕ci Di,c zi F 𝜕𝜕ci,r
+ 𝛻𝛻 � ci v − Di,c 𝛻𝛻ci − Di,c ci 𝛻𝛻 ln γi − ci 𝛻𝛻𝛻 + =0
𝜕𝜕𝜕 RT 𝜕𝜕𝜕
• Multi-species: Cl-, Ca+2, Na+, K+, Mg+2, OH-, SO4-2 , etc.
• Inter-species interactions are considered
• Can calculate pH, electrical conductivity (resistivity)
• Multi-mechanism: diffusion, advection, electrical migration, chemical activity
• Realistic modeling of actual transport processes

• Complex Input:
• Transport properties of all species (DCL, DNa, DOH, etc.),
• Boundary conditions (Surface concentration of all species)
• Environmental conditions (temperature, RH, moisture), etc.
• Complex solution:
• Advanced numerical techniques (e.g. FEM, FDM, etc.) are required

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 20

Multi-species/multi-mechanism
approach
𝜕𝜕ci 𝜕𝜕cis Di,c zi F
Transport: + + 𝛻𝛻 � (−Di,c 𝛻𝛻ci − Di,c ci 𝛻𝛻 ln γi − c 𝛻𝛻𝛻 + ci 𝑣𝑣) = 0 Boundary Conditions
𝜕𝜕𝜕 𝜕𝜕𝜕 RT i
• Solve for Cl-, Ca+2, Na+, K+, Mg+2, OH-, SO4-2 , etc. concentrations

Heat transfer:

• Solve for temperature profiles At every point in

domain and at
Moisture transfer: every time step of
the analysis
• Solve for RH and moisture profiles

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 21

Multi-species/multi-mechanism
approach
𝜕𝜕ci 𝜕𝜕cis Di,c zi F
Transport: + + 𝛻𝛻 � (−Di,c 𝛻𝛻ci − Di,c ci 𝛻𝛻 ln γi − c 𝛻𝛻𝛻 + ci v) = 0 Boundary Conditions
𝜕𝜕𝜕 𝜕𝜕𝜕 RT i

Heat transfer:

Moisture transfer:

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 22

Can we simplify?
𝜕𝜕ci Di,c zi F 𝜕𝜕ci,r
+ 𝛻𝛻 � ci v − Di,c 𝛻𝛻ci − Di,c ci 𝛻𝛻 ln γi − ci 𝛻𝛻𝛻 + =0
𝜕𝜕𝜕 RT 𝜕𝜕𝜕

2) Assume all these transport 3) Chloride binding

mechanisms can be simulated can be
through a diffusion-type (Fickian) incorporated to the
1) Ignore all ions, but Cl- approach. transport process.

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 23

What do we get?
𝜕𝜕ci Di,c zi F 𝜕𝜕ci,r
+ 𝛻𝛻 � ci v − Di,c 𝛻𝛻ci − Di,c ci 𝛻𝛻 ln γi − ci 𝛻𝛻𝛻 + =0
𝜕𝜕𝜕 RT 𝜕𝜕𝜕

𝜕𝜕cCl
+ 𝛻𝛻 � DCl 𝛻𝛻cCl = 0
𝜕𝜕𝜕

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 24

What do we get?
𝜕𝜕cCl
+ 𝛻𝛻 � −DCl 𝛻𝛻cCl = 0
𝜕𝜕𝜕
• Relatively simple input:
• Transport properties of chloride (DCL)
• Boundary conditions (surface concentration of chloride)
• Environmental conditions (temperature, RH, moisture), etc.
• Easy solution:
• Simple numerical solutions (FEM, FDM, etc.)
• With simplifications closed-form solution possible

• Single-species analysis: Cl-

• Cannot consider inter-species interactions
• Does not provide additional information such as pH, electrical conductivity, etc.
• Single transport mechanism: diffusion
• Simplified modeling of multiple transport processes

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 25

A note on DCl

Cl

Time dependent empirical modifiers

Reference diffusion coefficient (temperature, RH, time of exposure)
(at Tref, fully saturated)

From lab testing of

concrete specimens
From empirical From past
that are
OR equations from OR experience
representative of the
literature
concrete used in the
modeled structure

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 26

Simplify more?
• 1 D in the x-direction (might be possible for many structures; e.g. bridge decks, etc.)
• Constant diffusion coefficient (pretty big approximation)
• Assuming constant surface chloride concertation over time (pretty big approximation)

𝜕𝜕cCl 𝜕𝜕2cCl
= DCl
𝜕𝜕𝜕 𝜕𝜕𝑥𝑥2
• Closed-form solution is possible (no need for numerical methods)

𝑥𝑥
cCl (𝑥𝑥, 𝑡𝑡) = cs − cs − ci erf
4𝐷𝐷𝐶𝐶𝐶𝐶𝑡𝑡
Surface chloride concentration

Initial (background) chloride concentration

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 27

 David Trejo
David.Trejo@oregonstate.edu
O. Burkan Isgor
Burkan.Isgor@oregonstate.edu

OSU Doctoral Short Course (Trejo/Isgor) July 10-14, 2017 Slide 28