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
Innovations in Chemical (15) patents for concrete and masonry admixtures, and has authored over 30
publications in the field of analytical chemistry of cementitious systems and the

Admixture Technology as Related 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 Sub-
to Sustainability Committee 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
ACI Spring 2012 Convention achievements in the field of concrete admixture technology. Ara holds a Ph.D.
March 18 – 21, Dallas, TX degree in Analytical Chemistry from the University of Massachusetts.
ACI ACI
WEB SESSIONS 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
Chemical Admixtures of the Future: Opportunities and Performance
Challenges for Sustainable Concrete Production,  Admixture for Pervious Concrete
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 GRACE

Consulting the Admix Genie Role of Chemical Admixtures

in Concrete Construction
Ah…yes…
The Future of
Chemical
Admixtures………
Are you ready??

GRACE GRACE
 Addressing Concrete Durability Issues
Latest Innovations in Admixture Technology
Challenges Solution Strategies
(over the past 10 years)  Brittleness - cracking  Improve ductility - Macro fibers
Polycarboxylate-based Superplasticizers  Reduce shrinkage – SRA
PCs for Self-Compacting Concrete Dimensional stability
  Improve curing (self-curing) - Polyacrylics
Shrinkage Reducing Admixtures
– Thermal and hydration
ASR Control Agents  Reduce permeability
Admixtures for CLSM (Controlled Low Strength Material) – Admixtures to lower w/c - Superplasticizers
Hydration Stabilizing Agents for Returned Concrete  Permeability – water – Reactive Void Fillers - Microsilica, limestone
Antifreeze Admixtures (non-corrosive, alkali-free) transport – Integral waterproofing - Stearates
Viscosity Modifying Admixtures
– ASR & DEF  QC of raw materials – Paste Calorimetry
Anti-washout Admixtures
Slump Extending Admixtures – Sulfate attack
 Freeze-Thaw - Air entrainment w/
Nano-Admixtures for High Early Strength – Corrosion Surfactants, Wood Rosins, Tall Oil
Admixtures for Pervious Concrete
– Freeze/thaw  Corrosion Inhibitor– Calcium Nitrite
Surface Enhancing Admixtures
 ASR – Lithium Salts

GRACE GRACE

Chemical Admixture Wish List

A water reducing admixture that demonstrates uniform performance
Effect of Water Reduction on Concrete
with all cements or cement/SCM combinations. Cement dispersion is the most important and extensively used technical
An admixture which can perform as a normal, mid- and high range capability chemical admixtures provide in producing sustainable quality
water reducer - “linear dose/slump response with neutral set.” concrete mixtures.
Will the slump cone be replaced
A simple test that can alert concrete producers to a possible cement- Compressive Strength or Permeability = k/(w/c)3
by a hand-held rheometer??
admixture “incompatibility.”
An admixture that “cools” concrete
 Universal Air Entrain System for Garaunteed Air Content

Admixture systems that allow higher replacement levels (50% +)

of Portland cement with SCMs. WR
An admixture that facilitates production and significantly
increases robustness of SCC – reduces concern for failed loads. MRWR

Integral curing admixture.

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

Particle Size Distribution, ASTM C 150 T-I Cement Photomicrograph – Cement Dispersing Action of
Superplasticizers
The PSD for essentially all Portland Cements have
a trade off for strength versus water demand.

3– 30 m
ideal for
strength
with
minimal
Increased impact on
water water
demand demand
<1  m

Increased water
demand Higher particle
surface area –
Less than optimum
GRACE strength development
increased strength
 Technical Performance: Superplasticizers
Benefits of Superplasticized Concrete
Unexpected Performance Changes in
Mix Proportions, kg/m3 Cementitious Systems
Reference High Flowing Cement •Cement Chemistry
Strength Concrete Reduced
Mix - Kiln fuels, interground additions, variable
Cement 356 356 356 267
Sand 712 742 772 845
forms of gypsum
Stone 1127 1216 1068 1187
Water 178 133 178 133
•Supplementary Cementitious Materials
Superplasticizer, - 0.9 0.9 0.6
l/m3
- Fly ash, slag, silica fume, metakaolin
W/C 0.50 0.38 0.50 0.50
Slump, mm 115 125 240 125
•Chemical Admixture

Compressive
- More complex formulations
Strength, MPA - Multiple Admixtures (i.e. WRA, HRWR, AEA, Accel)
1-day 9.7 19.2 11.9 10.5
7-day 28.3 39.4 31.2 29.5
28-day 35.3 46.8 38.3 36.8 ASTM Sub-committee C01.90.02/C09.90 Joint Task Group
on PASTE SYSTEM PERFORMANCE
WR/MRWR/HRWR reduce cement, water, heat, porosity, & shrinkage GRACE

Portland Cement Clinker

Probing Cement-Admixture Issues with Calorimetry

Water/cement ratio 0.5, 23 C, 5 Cement Samples

water only
From Same Plant
- with reported
setting time
problems - Tested
Sulfate
depletion Without Admixtures

Water/cement ratio 0.5,

23 C, 1.0% water
MAJOR COMPOUNDS IN PORTLAND CEMENT reducing admixture by
weight of cement in all
samples
Mineral Cement Mass
Compound Phase Chemical Formula Notation
Range, %
Tricalcium silicate alite 3 CaOSiO2 C3S 25 - 65
Dicalcium silicate
Tricalcium aluminate
Tetracalcium aluminoferrite
belite
aluminate
ferrite
2 CaOSiO2
3 CaOAl2O3
4 CaOAl2O3Fe2O3
C2S
C3A
C4AF
10 - 50
3 - 12
8 - 14
+ With Admixtures

Sodium/potassium sulfate Alkalis

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

Typical Slump vs Set Response for SCMs Can Provide a Multitude of Benefits
various WRAs for Concrete Properties
Slump vs Set: Water Reducing Performance in Concrete
10

9
• Decreased Permeability
mm
8
• Reduced Sulfate Attack
225
7 • Reduced Efflorescence
200
6 Next • Reduced Shrinkage
Gen. PC
Slump, in

175
5
WRA Lignin
• Reduced Heat of Hydration
1504 Corn syrup
• Reduced Alkali Silica Reactivity
1253 NSFC • Increased Workability and Slump
100
2
Retention
75
1
• Improved Finishing
0
0 2 4 6 8 10 12 14 • Reduced Bleeding
Set Time, hr.min
• Reduced Segregation
SEM, 3600 X:1-day Concrete with Fly Ash
Slope [slump/set] = F[WRA dose,chemistry] and Silica Fume

Then, why aren’t SCMs used consistently

GRACE at 40-50% cement replacement ?? GRACE
Exploiting the wonderful World of Polycarboxylates
Understanding Structure-
Making flocculated hydrating cement Performance Correlation critical
to Leverage Value of PC
particles disperse Technology

Teeth length
Polycarboxylate Comb Polymer can be
designed for :
Teeth
•High early strength density

•Quick slump gain Polycarboxylates

CH2 CH

•Variable viscosity at same yield stress

C
a
O
CH2 CH

C
b
O
CH2 CH

C
c
O
CH2

O
CH

C
CH2 CH

C
d
O
are to concrete as
OH O
NH3
NH
N
designer drugs are
•Long Slump life without extended set H3C CH
H3C CH
H3C CH

CH2
CH2
CH2

O
to medicine
O
O
CH2
CH2
CH2
CH2
CH2
CH2 x
x
x O
O
O
H3C CH
H3C CH
H3C CH
CH2
CH2
y
CH2 y OCH3
y OCH3
OCH3
Backbone length

Time Release PCs: Extending Slump Life without Retardation Slump Retaining Admixture vs HSA (Hydration Stabilizing
PC4: Variable Dose Slump Retaining Polymer
Admixture)
for Extended Slump Life
Rapid Slump Loss Cement
10 120 420

4oz HSA
9 360
+ PC4, 2x 100
3oz HSA

Retardation from Control Mix (min)

mm Cement 445 kg/m3 300
8 2oz HSA
225
Stone 745 kg/m3
Slump (inch)

Slump Retention (%)

80
1oz HSA Control
240
7 200 7 oz/cwt + HSA
Sand 1000 kg/m3
175 60 PC-HRWR 180
6 +PC4, 1x Water 175 kg/m3 SRD
150
PC1 5:45 120 EXP.SRD (High Dose)
w/c 0.39 40 (Low Dose)
5 125 5:30
60

4
100
PC4 4:50 20 Control
0
0 30 60 90 120 150
3 0 -60
0 30 60 90 120 80% Slump Retention Time (min)
2 Elapsed Time (min)

0:00 0:15 0:30 0:45 1:00 1:15 1:30 1:45 2:00

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

Consequence of Retempering

Chemical “Admixtures” for Sand

Adding 5 liters/m of water
Caution: If you retemper, concrete will:
the concrete will • Increase slump by 25 mm

remember! • Decrease strength by 1.4 mpa

• Waste 11 kg cement
• Increase shrinkage potential
by about 10%
• Decrease F/T resistance by
Note difference in 20%
paste color

GRACE GRACE
 Clay Mitigating Admixture
Effect of Manufactured Sands and Viscosity Aggregate Production: Sand and Gravel
Modifying Admixture (VMA) on Pump Pressure
Pump Pressure as a Function of
% Manufactured Sand
20 Crushing

Goodquarry.com
18
coarse
16 Wet Screening
Pit (Dig or Washing/ products
Pump Pressure, MPa

14 Dredge) Screening
12
10 Mix Design, kg/m3
VMA, 3 ml/100kg Sand fine
8
Cement 248

Goodquarry.com
fresh Classifier products
6 (washing/sizing)
water
4
Fly Ash 65 Cyclone (sand classifier)
0.92 1.02 flocculent
1.0 recycled
2 Water 178 – 186 kg/m3 water Pond/
0 Lagoon
0 20 40 60 80 100 WRA 260 ml/100 kg

Goodquarry.com

Metso Minerals
% Manufactured Sand Slump 115-127 mm waste fines/clay
Sand/Stone
Settling Pond
Screw (sand classifier)
GRACE Note: Individual plant operation/layout may vary widely.

Limits on Clay in Concrete Aggregate CMA – Clay Mitigating Admixture

(United States) Impact on MBV Value
 ASTM C 33 Standard Specification for Concrete
Na-Montmorillonite Aggregates
240
– Material finer than 75 m
220
 <3-5% for sand and gravel
NSFC, 0.37%
Flow(mm)

200
 <5-7% for manufactured sand
180 – Clay lumps and friable particles
PCP, 0.13%
160
 3% max
 Sand Equivalent (ASTM D 2419) or Durability Index
140
Test (ASTM D 3744 or California 227 and 229)
0 0.5 1 1.5
Clay in Sand(%)
– Typically requires lower clay than ASTM C33
limits
– Does not distinguish effectively between clay
The Methylene Blue and non-clay fines
test provides direct
 Methylene Blue Value (not commonly specified)
measure of clay
content. – Simple and effective test for predicting effect of
Clays can be present
clays in natural
on HRWR demand or manufactured sands.
32 Grace Confidential

Impact of CMA on Mortar Flow New UV-Methylene Blue Test

Mortar Mix = 450 g cmt/1400 g sand/0.2% Clay/ 0.50w/c; 0.12% PC  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
w/o clay 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
Titration Method
New UV Method
Gradual titration end point determined
Methylene blue solution after mixing with
upon appearance of blue halo.
clay-bearing sand, ready for UV
measurement.
Methylene blue is a function of clay
content and clay activity.

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.
 Concrete Recycling w/ Hydration Stabilizing Admixture
Chemical Admixtures
Slurry Density Meter Readings for Pervious Concrete
Control HSA Dosage

J
E
F
B

C I
D G

A H Rain water etc.

A Coarse aggrgate screen F Slurry density meter

B Sand separator G Washing water tank
C Spiral separator H Slurry storage tank
D Admixture Tank I Reservoir
E Admixture dispenser J Mixer

GRACE

Concrete Admixtures for Pervious Concrete

 Maximize Compaction & Flowability
(HRWR/VMA/Retarder) Importance of Paste Drain
– Strength related mainly to voids content (aggregate Example of pervious concrete mixture with water content too high,
compacted voids content and paste volume), much
less to paste strength (w/cm, silica fume)
resulting in sealed surface.
– High compactability needed for consistent
performance (field compaction sometimes minimal)
– High compactability expected to correspond to fast
truck unloading
 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)

GRACE GRACE

Impact of HRWR and VMA on Fluidity and Chemical Admixtures based on Nano-particles
Voids Content The reactivity associated with the increased surface area has a
• Increasing HRWR reduced void content but • In contrast, viscosity modifying admixture potent strength accelerating impact on cement hydration
increased paste drain. reduced void content without an associated
• Acceptable at a dose of 0.05%s/c but large increase in paste drain.
excessive at a dose of 0.10%s/c. • VMA used in study is known to impart shear
• Paste drain was reduced by reducing w/c, but thinning rheology and enable use of poorly
voids content is increased. shaped aggregates.

6 Paste Drain 28.0 6 29.0

Void Content
Paste Drain
Void Content
5
5 28.5
27.5
2 Lifts at 5 Drops/Lift
2 lifts at 5 drops/lift
Void Content (%)

Void Content (%)

Paste Drain (%)

4
Paste Drain (%)

4 28.0

3 27.0
3 27.5

2
2 27.0
26.5
1
1 26.5

0 26.0
HRWR 0%s/c, 0.05%s/c, 0.1%s/c, 0.1%s/c, 0 26.0
w/c=0.26 w/c=0.252 w/c=0.243 w/c=0.22 0 0.0026%s/c 0.0039%s/c 0.0104%s/c

HRWR Dose and w/c VMA Dose (w/c=0.26)

GRACE
 Nano Admixtures promote cement hydration in the pore volume to
Nano Seed/ Particles for Concrete compliment topochemical reactions on cement surface
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.

GRACE 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% 8

0.48% 7

5075
Nano-Admix,
6 0.98% s/s
4650 Control
5
2500
3625
psi 4

Nano-admix, 0.49% s/s Control

3
2175

1550 2

725 1

0
-1 1 3 5 7 9 11 13 15
Nano-admixtures allow reaching strength targets at Hours

considerably earlier ages.

Position and intensity of main exotherm hydration peak
significantly modified
GRACE GRACE

Automated Slump Control:

In -Transit Water and Superplasticizer Adjustments
Compressive Strength Data (mpa),
Effect of Nano-Admix 10

Mpa 6 hr % Ref 9 hr % Ref 12 hr %Ref 24 hr %Ref 672 hr  Slump on target,

 Re-dose upon begin placement
8
Blank 2.9 100 7.8 100 12.3 100 25.2 100 slump loss
Slump, in.

150 mm
5.1 175.9 11.8 151.3 17.7 143.9 30.3 120.2 delivery
Nano-Admix 6  With water slump target
Nano-Admix 7.3 251.7 15.4 197.4 21.3 173.2 33.5 132.9 adjusted, begin
admixture dosing
 Delivery target slump achieved
4
batch
50 mm target
2
Nucleating effect from Nano-admixture capable of 2X  Batch slump too low, add water
Admixture (gal/10)

impact on early age compressive strengths (22 C). 0

plant transit jobsite
20
Water (gal)

Nano-admixtures have the capability of allowing admixture

10
increased use of SCMs, reduced heat curing, and
reducing cement contents. water
0
12:00 12:30 13:00 13:30 14:00

Batch slump used to ensure proper water content (strength)

Admixture adjusted to delivery slump target (contractor)
GRACE
 Some final thoughts:
Thank You!
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.

GRACE GRACE