Supplementary Cementitious Materials for Mitigating Kraft Pulp Fiber-Cement

Composite Degradation

Benjamin Mohr1, Joseph Biernacki2, Kimberly Kurtis1

Conclusions

Motivation Definition of Wet/Dry Cycle• Fiber-cement composites have been called

“tomorrow’s growth product.”1

• Low cost, non-hazardous replacement for asbestos-cement building components that are still used in developing countries.

• Influence of exterior exposure (i.e., heat/rain or wet/dry cycles) on composite performance has not been well-established.

• If pulp fiber-cement composites are to be used for exterior structural applications, the effects of wet/dry exposure must be known.

• To perform mechanical testing and microscopy to assess the durability of pulp fiber-cement composites to repeated wet/dry cycling.

• To identify those supplementary cementitious materials (SCMs) are effective at minimizing or preventing composite degradation due to wet/dry cycling.

• To establish the mechanisms for degradation mitigation in kraft-SCM composites.

100 μm100 μm

1 Kurpiel, F.T., “Fiber-cement siding is tomorrow’s growth product”, Wood Technology 1998;125(1):50-54.

Flexure Testing Results

1. Oven dried at 60° C for 23 ½ hours

2. Air dried at 20° C for 30 minutes to reach equilibrium

3. Soaked in water at 20° C for 23 ½ hours

4. Air dried at 20° C for 30 minutes to reach equilibrium

The cycle length was chosen based on trials of mass change over time. The upper bound of the curve was determined by soaking; the lower bound was determined by oven drying. At 72 hours, there was approximately 2% further mass change compared to 24 hours.

Mechanical Testing Program

• All samples were cured in limewater prior to wet/dry cycling.

• To eliminate the effects of age and improving matrix strength with time, all samples were tested at 78 days regardless of the number of wet/dry cycles. For example, for 25 cycles, 28 day curing was followed by 50 days of wet/dry cycling.

1”x1”x4” beams (3” span) Fiber-reinforced cement beams tests in three-point bending.

LoadPost-cracking Toughness

Deflection

Composites containing 30% SF, 50% SF, 90% SL, and 30% MK235 completely eliminated degradation due to wet/dry cycling. However, all but the SL composite are not practical for large-scale production.

Ternary and quaternary blends of 10% SF/70% SL, 10% MK235/70% SL, and 10% MK235/10% SF/70% SL also completely eliminated composite degradation at more practical replacement values.

Composite pore structure and permeability do not seem have an effect on durability for these cast-in-place composites.

It is thought that certain SCMs are effective in mitigating composite degradation through several processes, including a reduction in the calcium hydroxide content, stabilization of monosulfate by maintaining pore solution pH, and minimization of ettringite reprecipitation through the binding of aluminum in calcium aluminates.

1 School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, GA2 Department of Chemical Engineering, Tennessee Technological University, Cookeville, TN

AcknowledgementsThe authors gratefully acknowledge financial support from the National Science Foundation under CMS-0122068 and DMR-0115961, Institute of Paper Science and Technology seed grants, and PATHWAYS grant.

0

5

10

15

20

25

30

35

0 4 8 12 16 20 24Time (hr)

Per

cen

t m

ass

chan

ge

Fiber AFiber BFiber CFiber D

Proposed Kraft Pulp Fiber Composite Degradation Mechanism

0.1

1

10

100

0 5 10 15 20 25Number of Wet/Dry Cycles

Ave

rag

e P

ost

-cra

ckin

g

To

ug

hn

ess

(lb

f-in

)

No matrix modifications10% silica fume replacement30% silica fume replacement50% silica fume replacement

0.1

1

10

100

0 5 10 15 20 25Number of Wet/Dry Cycles

Ave

rag

e P

ost

-cra

ckin

g

To

ug

hn

ess

(lb

f-in

)

No matrix modifications 10% slag replacement30% slag replacement 50% slag replacement70% slag replacement 90% slag replacement

0.1

1

10

100

0 5 10 15 20 25Number of Wet/Dry Cycles

Ave

rag

e P

ost

-cra

ckin

g

To

ug

hn

ess

(lb

f-in

)

No matrix modifications10% Class C fly ash replacement30% Class C fly ash replacement50% Class C fly ash replacement70% Class C fly ash replacement

0.1

1

10

100

0 5 10 15 20 25Number of Wet/Dry Cycles

Ave

rage

Pos

t-cra

ckin

g To

ughn

ess

(lbf-i

n)

No matrix modifications10% Class F fly ash replacement30% Class F fly ash replacement50% Class F fly ash replacement70% Class F fly ash replacement Generally, all SCM replacements by weight of

cement led to improved wet/dry cycling composite post-cracking toughness durability.

Silica fume replacements of 30 and 50% as well as slag replacement of 90% prevented any composite degradation due to cycling.

Ternary and quaternary pozzolanic fiber-cement composites have also been investigated to optimize cost and performance.

SCM particle size (i.e., DEVA and MK varying in particle size only) does not appear to play a role in composite degradation. Thus, matrix permeability may not be a contributing factor.

Research Objectives

1. Initial fiber-cement / fiber interlayer debonding.2. Reprecipitation of crystalline or amorphous ettringite in void space

created by step (1).3. Fiber embrittlement due to reprecipitation of calcium hydroxide

(CH) within kraft pulp fiber cell wall structure.

0.0

0.1

0.2

0.3

0.4

0.5

0.0 0.1 0.2 0.3 0.4 0.5S/Ca

Al/C

a

0 cycles1 cycle2 cycles25 cyclesCH + EttringiteCH + Monosulfate

0.0

0.1

0.2

0.3

0.4

0.5

0.0 0.1 0.2 0.3 0.4 0.5S/Ca

Al/C

a

0 cycles1 cycle2 cycles25 cyclesCH + EttringiteCH + Monosulfate

Minimal debonding inhibits ettringite reprecipitation

around TMP fibers.

0.1

1

10

100

0 5 10 15 20 25Number of Wet/Dry Cycles

Ave

rag

e P

ost

-Cra

ckin

g

To

ug

hn

ess

(lb

f-in

)

No matrix modifications10% MK235 replacement30% MK235 replacement10% MK349 replacement30% MK349 replacement

0.1

1

10

100

0 5 10 15 20 25Number of Wet/Dry Cycles

Ave

rag

e P

ost

-Cra

ckin

g

To

ug

hn

ess

(lb

f-in

)

No matrix modifications10% DEVA (calcined) replacement30% DEVA (calcined) replacement50% DEVA (calcined) replacement

0.1

1

10

100

0 5 10 15 20 25Number of Wet/Dry Cycles

Ave

rag

e P

ost

-Cra

ckin

g

To

ug

hn

ess

(lb

f-in

)

No matrix modifications10% DEVA (raw) replacement30% DEVA (raw) replacement50% DEVA (raw) replacement

0.0

0.1

0.2

0.3

0.4

0.5

0.0 0.1 0.2 0.3 0.4 0.5S/Ca

Al/

Ca

No SCMs10% slag50% slag90% slagCH + EttringiteCH + Monosulfate

0.0

0.1

0.2

0.3

0.4

0.5

0.0 0.1 0.2 0.3 0.4 0.5S/Ca

Al/

Ca

No SCMs10% silica fume50% silica fumeCH + EttringiteCH + Monosulfate

0

20

40

60

80

100

120

140

0.1 1 10 100Toughness (25 cycles)

CH

En

thal

py

(J/g

)

Chemical / EDS Analysis (after 25 cycles)

Differential Scanning Calorimetry (DSC)

0.00

0.05

0.10

0.15

0.20

0.25

0.0 0.2 0.4 0.6 0.8 1.0Si/Ca

(K+

Na

)/C

a

No SCMs10% silica fume50% silica fume

0.00

0.05

0.10

0.15

0.20

0.25

0.0 0.2 0.4 0.6 0.8 1.0

Si/Ca

(K+

Na)

/Ca

No SCMs10% slag50% slag90% slag

The addition of SCMs reduced / prevented the reprecipitation of secondary ettringite and alkali leaching as observed by EDS.

The reduction in ettringite formation allows for continued net fiber swelling and shrinkage. Thus, CH reprecipitation within the fiber cell wall is minimized.

The presence of alkalis after 25 cycles indicates a maintaining of the pore solution pH, minimizing destabilization and conversion of monosulfate to ettringite.

The addition of SCMs led to a progressive decrease in matrix calcium hydroxide content prior to wet/dry cycling with increasing replacement amounts.

SCM composites that showed no degradation during cycling were found to have no calcium hydroxide.

There appears to be a direct correlation between matrix calcium hydroxide content prior to cycling and composite toughness after 25 wet/dry cycles.

Low calcium hydroxide content does not guarantee significant composite toughness. Thus, other factors described by chemical analysis also play an important role in the progression of degradation during wet/dry cycling.

Kraft pulp fibers

TMP fibers

Kraft pulp

TMP

Slag (SL) Class C fly ash (CA)

Metakaolin (MK)Silica fume (SF)

For TMP fibers, it is thought that lignin in the fiber cell wall acts as a barrier to CH reprecipitation. Thus, CH formation is limited to the fiber lumen.

Swollen state Shrunken stateCrystalline or amorphous ettringite formation

Fiber embrittlement