Innovations in Chemical Admixture Technology as Related to Sustainability

ACI Spring 2012 Convention March 18 21, Dallas, TX

ACI WEB SESSIONS

Ara A. Jeknavorian is a Research Fellow with the Construction Products Division of W.R. Grace in Cambridge, Massachusetts. Starting in 1979 with the Technical Service group, Dr. Jeknavorian conducted has numerous investigations on the performance of concrete materials and chemical admixtures, and has developed numerous chemical and instrumental methods for troubleshooting cementitious systems. In 1995, he began product development for chemical admixtures, spearheading the introduction of polycarboxylate-based superplasticizers to N. America. He is an inventor on twelve (15) patents for concrete and masonry admixtures, and has authored over 30 publications in the field of analytical chemistry of cementitious systems and the application of chemical admixtures for concrete. Dr. Jeknavorian is a member of the American Chemical Society, American Concrete Institute, and the ASTM C09 Committee on Concrete, where he has chaired the Chemical Admixtures SubCommittee and has been recognized for outstanding service for his contribution to standards development for chemical admixtures. At the Sixth CANMET/ACI International Conference on Superplasticizers and Other Chemical Admixtures (Nice 2000), Dr. Jeknavorian received recognition for outstanding contributions and achievements in the field of concrete admixture technology. Ara holds a Ph.D. degree in Analytical Chemistry from the University of Massachusetts.

ACI WEB SESSIONS

Outline

Recent Innovations in Admixture Technology Chemical Admixture Wish List Wonderful World of Polycarboxylates Dial-in Slump Retention with Time-Release PCE Admixtures For Aggregates Nano Admixtures for Accelerated Strength Performance Admixture for Pervious Concrete

Chemical Admixtures of the Future: Opportunities and Challenges for Sustainable Concrete Production, Placement, and Service Life Ara A. Jeknavorian, Ph.D., Research Fellow W.R. Grace & Co., Cambridge, MA USA
"Innovations in Chemical Admixture Technology as Related to Sustainability ACI Spring 2012 Convention - Dallas ACI Committee 212 on Chemical Admixtures

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Consulting the Admix Genie

Role of Chemical Admixtures in Concrete Construction

Ahyes The Future of Chemical Admixtures Are you ready??

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Latest Innovations in Admixture Technology (over the past 10 years)

Polycarboxylate-based PCs

Addressing Concrete Durability Issues

Challenges
Brittleness - cracking

Solution Strategies
Improve ductility - Macro fibers Reduce shrinkage SRA

Superplasticizers for Self-Compacting Concrete Shrinkage Reducing Admixtures ASR Control Agents Admixtures for CLSM (Controlled Low Strength Material) Hydration Stabilizing Agents for Returned Concrete Antifreeze Admixtures (non-corrosive, alkali-free) Viscosity Modifying Admixtures Anti-washout Admixtures Slump Extending Admixtures Nano-Admixtures for High Early Strength Admixtures for Pervious Concrete Surface Enhancing Admixtures

Dimensional stability
Thermal and hydration

Improve curing (self-curing) - Polyacrylics Reduce permeability

Admixtures to lower w/c - Superplasticizers Reactive Void Fillers - Microsilica, limestone Integral waterproofing - Stearates QC of raw materials Paste Calorimetry

Permeability water transport

ASR & DEF Sulfate attack Corrosion Freeze/thaw

Freeze-Thaw - Air entrainment w/

Surfactants, Wood Rosins, Tall Oil Corrosion Inhibitor Calcium Nitrite ASR Lithium Salts

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Chemical Admixture Wish List

A water reducing admixture that demonstrates uniform performance with all cements or cement/SCM combinations. An admixture which can perform as a normal, mid- and high range water reducer - linear dose/slump response with neutral set. A simple test that can alert concrete producers to a possible cementby a hand-held rheometer?? admixture incompatibility. An admixture that cools concrete

Effect of Water Reduction on Concrete

Cement dispersion is the most important and extensively used technical capability chemical admixtures provide in producing sustainable quality concrete mixtures.

Will the slump cone be replaced

Compressive Strength or Permeability = k/(w/c)3

Universal Air Entrain System for Garaunteed Air Content Admixture systems that allow higher replacement levels (50% +) of Portland cement with SCMs. An admixture that facilitates production and significantly increases robustness of SCC reduces concern for failed loads. Integral curing admixture.
HRWR MRWR

WR

Dial-in slump retention without extended set and independent of cement chemistry and temperature.

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Particle Size Distribution, ASTM C 150 T-I Cement

The PSD for essentially all Portland Cements have a trade off for strength versus water demand.
3 30 m ideal for strength with minimal impact on water demand

Photomicrograph Cement Dispersing Action of Superplasticizers

Increased water demand <1 m

Increased water demand

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Less than optimum strength development

Higher particle surface area increased strength

Technical Performance: Superplasticizers

Benefits of Superplasticized Concrete Mix Proportions, kg/m3 Reference High Strength 356 742 1216 133 0.9 0.38 125 Flowing Concrete 356 772 1068 178 0.9 0.50 240 Cement Reduced Mix 267 845 1187 133 0.6 0.50 125

Unexpected Performance Changes in Cementitious Systems

Cement Chemistry - Kiln fuels, interground additions, variable forms of gypsum Supplementary Cementitious Materials - Fly ash, slag, silica fume, metakaolin Chemical Admixture - More complex formulations - Multiple Admixtures (i.e. WRA, HRWR, AEA, Accel)

Cement Sand Stone Water Superplasticizer, l/m3 W/C Slump, mm Compressive Strength, MPA 1-day 7-day 28-day

356 712 1127 178 0.50 115

9.7 28.3 35.3

19.2 39.4 46.8

11.9 31.2 38.3

10.5 29.5 36.8

WR/MRWR/HRWR reduce cement, water, heat, porosity, & shrinkage

ASTM Sub-committee C01.90.02/C09.90 Joint Task Group on PASTE SYSTEM PERFORMANCE

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Portland Cement Clinker

Probing Cement-Admixture Issues with Calorimetry

Water/cement ratio 0.5, 23 C, water only

Sulfate depletion

5 Cement Samples From Same Plant - with reported setting time problems - Tested Without Admixtures

MAJOR COMPOUNDS IN PORTLAND CEMENT Mineral Compound Range, % Tricalcium silicate Dicalcium silicate Tricalcium aluminate Tetracalcium aluminoferrite Sodium/potassium sulfate Phase alite belite aluminate ferrite Alkalis Cement Chemical Formula C3S C2S C3A C4AF Mass Notation 25 - 65 10 - 50 3 - 12 8 - 14

Water/cement ratio 0.5, 23 C, 1.0% water reducing admixture by weight of cement in all samples

3 CaOSiO2 2 CaOSiO2 3 CaOAl2O3 4 CaOAl2O3Fe2O3

With Admixtures

Inter-ground Calcium Sulfate Gypsum, Plaster, and/or Annhydrite

Typical Slump vs Set Response for various WRAs

Slump vs Set: Water Reducing Performance in Concrete
10 9

SCMs Can Provide a Multitude of Benefits for Concrete Properties

Decreased Permeability Reduced Sulfate Attack Reduced Efflorescence Reduced Shrinkage Reduced Heat of Hydration Reduced Alkali Silica Reactivity Increased Workability and Slump Retention Improved Finishing Reduced Bleeding Reduced Segregation
SEM, 3600 X:1-day Concrete with Fly Ash and Silica Fume

mm 8 225 200
Slump, in

7 6

175

Next Gen. WRA

PC Lignin Corn syrup NSFC

4 150 3 125

100
1

75

0
0 2 4 6 8 10 12 14 Set Time, hr.min

Slope [slump/set] = F[WRA dose,chemistry]

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Then, why arent SCMs used consistently at 40-50% cement replacement ?? GRACE

Exploiting the wonderful World of Polycarboxylates

Making flocculated hydrating cement particles disperse

Polycarboxylate Comb Polymer can be designed for : High early strength Quick slump gain Variable viscosity at same yield stress
a b C O C O OH CH2 CH CH2 CH CH2 CH C NH H3C CH CH2 CH2 O O CH2 CH2 CH2 x O O H3C H3C CH CH2 y OCH3 CH2 y OCH3 CH H3C CH2 x H3C CH2 c O O CH C N CH CH2 O CH2 CH2 x O CH CH2 y OCH3 CH2 CH C d O O NH3 CH

Understanding StructurePerformance Correlation critical to Leverage Value of PC Technology

Teeth length

Teeth density

Long Slump life without extended set

H3C

Polycarboxylates are to concrete as designer drugs are to medicine

Backbone length

Time Release PCs: Extending Slump Life without Retardation

PC4: Variable Dose Slump Retaining Polymer
10 9 8
mm 225 200 175

Slump Retaining Admixture vs HSA (Hydration Stabilizing Admixture) for Extended Slump Life
Rapid Slump Loss Cement
420 360 120

4oz HSA

Cement Stone Sand

445 kg/m3
Slump Retention (%)

Retardation from Control Mix (min)

+ PC4, 2x

100

3oz HSA 2oz HSA 1oz HSA 7 oz/cwt PC-HRWR

300 240 180 120 60 Control 0 0 30 60 90 120 150 EXP.SRD (Low Dose) SRD (High Dose) Control + HSA

Slump (inch)

745 kg/m3 1000 kg/m3 175 0.39 kg/m3

80

7 6 5 4 3

+PC4, 1x PC1 PC4 4:50 5:30

60

150 125 100

5:45

Water w/c

40

20

0 0 30 60 Elapsed Time (min) 90 120

-60 80% Slump Retention Time (min)

2 0:00

0:15

0:30

0:45

1:00

1:15

1:30

1:45

2:00

Elapsed Time

HSA is an option to extend slump life, but with the capability of significantly extended set retardation.

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Consequence of Retempering Chemical Admixtures for Sand

Caution: If you retemper, the concrete will remember!

Adding 5 liters/m of water concrete will: Increase slump by 25 mm Decrease strength by 1.4 mpa Waste 11 kg cement Increase shrinkage potential by about 10%

Note difference in paste color

Decrease F/T resistance by 20%

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Effect of Manufactured Sands and Viscosity Modifying Admixture (VMA) on Pump Pressure
Pump Pressure as a Function of % Manufactured Sand
20 18 16 Pump Pressure, MPa 14 12 10 8 6 4 2 0 0 20 40 60 80 100 % Manufactured Sand

Clay Mitigating Admixture Aggregate Production: Sand and Gravel

Crushing

Pit (Dig or Dredge)

Washing/ Screening

coarse products

Wet Screening

Mix Design, kg/m3

VMA, 3 ml/100kg fresh water recycled water
(washing/sizing)
Goodquarry.com Metso Minerals

Cement Fly Ash

248 65

Sand Classifier

fine products
Cyclone (sand classifier)

0.92

1.0

1.02

flocculent Pond/ Lagoon waste fines/clay

Settling Pond
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Water 178 186 kg/m3 WRA 260 ml/100 kg

Sand/Stone

Slump 115-127 mm

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Screw (sand classifier)

Note: Individual plant operation/layout may vary widely.

Limits on Clay in Concrete Aggregate (United States)

Na-Montmorillonite
240

CMA Clay Mitigating Admixture

Impact on MBV Value

ASTM C 33 Standard Specification for Concrete Aggregates Material finer than 75 m

220

<3-5% for sand and gravel <5-7% for manufactured sand

NSFC, 0.37%
Flow(mm) 200

180

Clay lumps and friable particles

PCP, 0.13%

160

3% max

140 0 0.5 1 Clay in Sand(%) 1.5

Sand Equivalent (ASTM D 2419) or Durability Index Test (ASTM D 3744 or California 227 and 229) Typically requires lower clay than ASTM C33 limits Does not distinguish effectively between clay and non-clay fines

The Methylene Blue test provides direct measure of clay content.

Methylene Blue Value (not commonly specified)

Simple and effective test for predicting effect of Clays can be present in natural or manufactured sands. clays on HRWR demand
32 Grace Confidential

Impact of CMA on Mortar Flow

Mortar Mix = 450 g cmt/1400 g sand/0.2% Clay/ 0.50w/c; 0.12% PC w/o clay

New UV-Methylene Blue Test

Methylene blue is a function of clay content and clay activity A novel test method was developed to expedite and improve MBV results
Existing titration method (e.g. AASHTO TP 57): titration test to determine amount of methylene blue solution absorbed by clay New Grace UV-MBV method: UV-vis measurement of methylene blue solution to determine methylene blue dye depletion for solution in presence of clay bearing aggregates

One mixing of methylene blue solution rather than gradual titration enables faster results Test is performed on entire sand sample, ensuring representative results
New UV Method Methylene blue solution after mixing with clay-bearing sand, ready for UV measurement. Methylene blue is a function of clay content and clay activity.

Titration Method Gradual titration end point determined upon appearance of blue halo.

Source: Yool, A.I.G., Lees, T.P., and Fried, A. (1998). Improvements to the Methylene Blue Dye Test for Harmful Clay in Aggregates for Concrete and Mortar Cement and Concrete Research, 28(10), 1417-1428.

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Concrete Recycling w/ Hydration Stabilizing Admixture

Slurry Density Meter Readings Control HSA Dosage
J
E

Chemical Admixtures for Pervious Concrete

F B C D A G H
A Coarse aggrgate screen B Sand separator C Spiral separator D Admixture Tank E Admixture dispenser Rain water etc. F Slurry density meter G Washing water tank H Slurry storage tank I Reservoir J Mixer

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Concrete Admixtures for Pervious Concrete

Maximize Compaction & Flowability (HRWR/VMA/Retarder) Strength related mainly to voids content (aggregate compacted voids content and paste volume), much less to paste strength (w/cm, silica fume) High compactability needed for consistent performance (field compaction sometimes minimal) High compactability expected to correspond to fast truck unloading

Importance of Paste Drain

Example of pervious concrete mixture with water content too high, resulting in sealed surface.

Reduce Paste Drain & Water Sensitivity (HRWR/VMA) Proper paste rheology needed to prevent paste collecting at bottom of section Enable paste composition with less cement, more water

Lengthen Curing Window (Retarder -VMA) Increase water content Retard cement hydration Bind water
b/b0=(agg compaction in concrete)/(maximum agg compaction)

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Impact of HRWR and VMA on Fluidity and Voids Content

Increasing HRWR reduced void content but increased paste drain. Acceptable at a dose of 0.05%s/c but excessive at a dose of 0.10%s/c. Paste drain was reduced by reducing w/c, but voids content is increased.
6
Paste Drain Void Content

Chemical Admixtures based on Nano-particles

The reactivity associated with the increased surface area has a potent strength accelerating impact on cement hydration

In contrast, viscosity modifying admixture reduced void content without an associated large increase in paste drain. VMA used in study is known to impart shear thinning rheology and enable use of poorly shaped aggregates.
6
Paste Drain Void Content

28.0

29.0

28.5

Paste Drain (%)

28.0

27.0

27.5

2 26.5 1

27.0

1
26.0 w/c=0.26 0.05%s/c, w/c=0.252 0.1%s/c, w/c=0.243 0.1%s/c, w/c=0.22

26.5

HRWR 0%s/c,

0 0 0.0026%s/c 0.0039%s/c 0.0104%s/c

26.0

HRWR Dose and w/c

VMA Dose (w/c=0.26)

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Void Content (%) 2 Lifts at 5 Drops/Lift

Void Content (%) 2 lifts at 5 drops/lift

27.5

Paste Drain (%)

Nano Seed/ Particles for Concrete

Calcium silicates Magnesium silicates Lime, CaO Hydrated Lime, Ca(OH)2 Calcium Carbonate, CaCO3 Titanium oxide, TiO2 Silica, SiO2 Iron Oxides Carbon nanotube All of these particles, when present in the nano-size range, have the ability to promote nucleation of cement hydration products, thus accelerating cement hydration process and strength gain.

Nano Admixtures promote cement hydration in the pore volume to compliment topochemical reactions on cement surface

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Seeding schematic (Thomas et al. 2009)

Isothermal Calorimetry of Mortar Mixes with Nano-Admixture

Opportunities to reduce heat curing or increase use of SCMs
9 24 Hr

Psi

0.96% 0.48%

5075

4650 3625 2500 psi

Control

Nano-Admix, 0.98% s/s

Nano-admix, 0.49% s/s

2175 1550
3

Control

725

Nano-admixtures allow reaching strength targets at considerably earlier ages.

-1

5 Hours

11

13

15

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Position and intensity of main exotherm hydration peak significantly modified

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Compressive Strength Data (mpa), Effect of Nano-Admix

Mpa
Blank Nano-Admix Nano-Admix

Automated Slump Control: In -Transit Water and Superplasticizer Adjustments

10

6 hr
2.9 5.1 7.3

% Ref
100 175.9 251.7

9 hr
7.8 11.8 15.4

% Ref
100 151.3 197.4

12 hr
12.3 17.7 21.3

%Ref
100 143.9 173.2

24 hr
25.2 30.3 33.5

%Ref
100 120.2 132.9

672 hr
8

Re-dose upon slump loss With water adjusted, begin admixture dosing

Slump on target, begin placement

delivery target

Slump, in.

150 mm

6 4 2 0

slump

Delivery target slump achieved

batch target

50 mm

plant

transit

jobsite

20 10

Nano-admixtures have the capability of allowing increased use of SCMs, reduced heat curing, and reducing cement contents.
12:00 12:30 13:00 13:30

admixture water
0 14:00

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Batch slump used to ensure proper water content (strength) Admixture adjusted to delivery slump target (contractor)

Water (gal) Admixture (gal/10)

Nucleating effect from Nano-admixture capable of 2X impact on early age compressive strengths (22 C).

Batch slump too low, add water

Some final thoughts:

Regardless of what new and exciting admixture technologies are introduced into the concrete industry, successful routine production of cost-effective, high quality, and sustainable concrete will greatly be facilitated by: Identify those parameters - materials, processes, structure design, and environment that can transform in spec concrete construction into a case for litigation. Learn how to predict and control those parameters keeping away from the edge of disaster.

Thank You!

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