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Technical Paper

Moisture Sensitivity of Asphalt Mixes Based on Surface


Chemistry of Aggregates and Asphalt Binders

Ayyanna Habal1 Dharamveer Singh2

ABSTRACT
In the present study, moisture sensitivity of different aggregates-asphalt binders was evaluated
using Surface Free Energy (SFE) approach. Three different asphalt binders: VG 30, PMB 40 and
CRMB 60, and two types of aggregates: granite and limestone were selected in this study. The SFE
components of the asphalt binders were measured using Wilhelmy plate method, while SFE of
granite and limestone aggregates were adopted from the literature. Thereafter, work of adhesion,
work of cohesion, work of debonding in presence of water, and energy ratio (ER) were calculated
to evaluate moisture sensitivity of asphalt-aggregate system. The results indicate that limestone
aggregate had a higher moisture resistant potential with all types of asphalt binders compared to
those of granite aggregate. Further, PMB 40 showed better bond with selected aggregates followed
by CRMB 60 and VG 30 asphalt binders. It was found that asphalt binder and aggregates types
can have a significant influence on moisture sensitivity of aggregates-asphalt binder system. It is
expected that the present study would be a positive step in direction of mechanistic evaluation of
moisture damage potential of asphalt mixes in India.
1. INTRODUCTION tests are developed to evaluate moisture damage
A flexible pavement is primarily constructed with of asphalt mixes. However; these tests provide a
bituminous mix composed of aggregates and gross estimate of cumulative effects of material
asphalt binders. This kind of pavement suffers and mixture properties on moisture sensitivity
different types of distresses such as stripping, of asphalt mixtures. None of these tests provide
raveling, moisture damage, cracking, rutting a better correlation with field performance of a
and pothole formation. The moisture damage is pavement. In addition, the tests are not adequate to
one of the primary reasons for premature failure explain mechanism which causes moisture damage
of most of flexible pavements. The moisture in asphalt mixes (Imad et al. 2014, Williams et al.
damage in asphalt mixes can be due to loss of 2010).
bond between aggregate and asphalt interface To overcome these shortcomings, recently many
known as adhesive failure or it can be a failure of researchers (Ghabchi et al 2013, Arbani et al. 2011,
bond between asphalt binder or mastic (mixture Bhasin et al. 2007, Little et al. 2007, Wasiuddin
of asphalt binder and aggregate fines passing et al. 2005, Hefer et al. 2005, Cheng et al. 2002,)
75 μm) known as cohesive failure (Little and Jones suggested Surface Free Energy (SFE) concept
2003). The surface chemistry of aggregate and to mechanistically evaluate moisture-induced
asphalt binders plays an important role to produce damage potential of asphalt mixes. The SFE approach
a moisture resistant mix. A number of laboratory is based on surface chemistry of materials, which
tests: Tensile Strength Ratio (TSR), Hamburg can be used to quantify bonding of aggregate-asphalt
Wheel Tracking (HWT), boiling and static water binder system. The SFE components of binders can
1
Ph.D. Student, Deptt of Civil Engg, I.I.T. Bombay, Mumbai-400 076, India E-mail: ayyanna.habal@gmail.com
2
Assistant Professor, Deptt. Civil Engg, I.I.T. Bombay, Mumbai-400 076, India, E-mail: dvsingh@iitb.ac.in

INDIAN HIGHWAYS, September 2017 11


Technical Paper

be estimated based on contact angle measured using 2. OBJECTIVES


Wilhelmy plate method. While, for aggregates, SFE The objectives of this study were to:
components are determined using Universal sorption
(a) Measure contact angle of VG 30, PMB 40 and
device. Wasiuddin et al. (2005) measured the SFE of
CRMB 60 asphalt binders using Wilhelmy plate
PG 70-28 and PG 64-22 using Wilhelmy plate device
method, and estimate their SFE components.
and suggested that SFE concept can be used to
develop new test methods for identifying moisture (b) Evaluate moisture sensitivity of limestone
damage susceptible mixes during mix design and granite aggregates in combination with
stage. Similarly, Hefer et al. (2006) studied the SFE VG 30, PMB 40 and CRMB 60 asphalt
components of asphalt binders using Wilhelmy plate binders based SFE approach.
method and determined compatibility of aggregates 3. BACKGROUND ON SURFACE FREE
with asphalt binders. It was reported that the SFE ENERGY
concept can be used to select most compatible asphalt The SFE of a material is defined as the magnitude of
binder and aggregate combination. In another study, work required to create a unit area of a new surface
Arbani et al. (2012) evaluated moisture susceptibility in a vacuum. The SFE is commonly denoted by the
of warm mix binders using SFE concept. They reported Greek letter ‘γ’. The units of SFE are ergs/cm2 or mJ/
that warm mix additive reduces the adhesion between m2 (Oss et al. 1988). According to acid-base theory
asphalt and aggregate. In recent study Ghabchi (Oss et al. 1988), SFE of any material is divided
et al. (2013) evaluated the effects of a warm mix- into three components namely: Lifshitz-van der
additive, on the SFE components of PG 64-22 asphalt Waals component (γLW), Lewis acid component (γ+),
binder using Wilhelmy plate method and found that and Lewis base component (γˉ). These components
this increases the SFE of asphalt binder and work are used together to estimate total SFE (γ) as per
of adhesion of asphalt binder – aggregates system. Equations 1 and 2.
In another study, Tian et al. (2013) conducted shear
strength and boiled tests to validate adhesion properties γ = γ LW+ γAB ... (1)
of asphalt binder and aggregate and suggested that the Where,
SFE theory can be used as a quantitative evaluation
method on asphalt and aggregate adhesion. γAB =  ... (2)
Currently, no study has been conducted in India to The work of cohesion (WBB) of asphalt binder can be
utilize the SFE approach for evaluating moisture calculated using Equation 3.
susceptibility of asphalt mixes. The literature showed
that same grade of bitumen or same type of aggregates WBB = 2γB ... (3)
from different sources may result in different surface Similarly work of adhesion between asphalt binder
free energy. Therefore, compatibility of aggregate- (B) and aggregate (A) is work required to separate
asphalt binder may change with source, chemical asphalt binder coating from aggregate surface at
composition, and type of aggregate/asphalt binder. their interface in vacuum (Little and Bhasin 2006)
Thus, the present study was undertaken to study expressed in Equation 4.
moisture sensitivity of VG 30, PMB 40 and CRMB
60 asphalt binders with different types of aggregates
(granite and limestone) using the SFE concept. The WAB =  ... (4)
selected unmodified and modified (polymer and
crumb rubber) binders and limestone and basalt Where, γLW, γ+, and γˉ are Lifshitz-van der Waals
aggregates are commonly used for construction of component, Lewis acid component and Lewis base
flexible pavements in India. Also, limestone and components respectively. Subscripts A and B indicates
basalt aggregates have different surface chemistry and Aggregate and Asphalt binder respectively.
chemical composition, and hence they were selected Water tries to separate asphalt binder coating from
in this study. The moisture sensitivity of six different aggregate, due to this action the total SFE of the
combinations of aggregate-asphalt binders (3 asphalt system reduces. The reduction of system energy in
binders x 2 aggregates) were evaluated in this study presence of water is known as work of debonding
based on the SFE approach. It is expected that the as shown in Equation 5.
present study would be a positive step in direction of
 ... (5)
mechanistic evaluation of asphalt mixes in India.

12 INDIAN HIGHWAYS, September 2017


Technical Paper

Where, γAW, γBW, and γAB are interfacial energy between angle (Hefer et al. 2006). In this method, a glass
aggregate-water, asphalt binder-water and aggregate- plate coated with asphalt binder is immersed into
asphalt binder respectively. a probe liquid and weight difference is measured
Bhasin et al (2006) suggested to estimate energy ratio with help of a high precision micro balance, which
(ER) of aggregate-asphalt binder system to evaluate is used to estimate dynamic contact angle (Hefer
moisture sensitivity. The ER is defined as ratio of et al. 2006). In this study, microscope cover glass
wettability (WAB-WBB) to the work of debonding plates of size 24 mm x 50 mm x No-1.5 were used
in presence of water as shown in Equation as substrates for preparing asphalt binder samples.
6. A higher value of ER, implies better moisture The glass plate was coated with selected asphalt
resistant mix and vice versa. binder (Fig. 3). Thickness of asphalt binder coating
over glass plate was measured using digital Vernier
ER =  ... (6) caliper, the average thickness was approximately
0.15 ± 0.02 mm for VG 30 and PMB 40 binders and
4. MATERIALS AND TEST METHODOLOGY it was 0.6 ± 0.02 mm for CRMB 60. Four replicate
In this study three types of asphalt binders: VG 30, of samples for each probe liquids (water, formamide
polymer modified binder, PMB 40 and crumb rubber and glycerol) were prepared and tested. Based on
modified binder, CRMB 60 commonly used in India contact angles measured from three probe liquids, the
for construction of flexible pavements were selected. SFE components of asphalt binders were estimated
In addition, two types of aggregates: limestone and using Equation 7. The results of contact angle and
granite were selected to evaluate their compatibility SFE components of asphalt binders are presented in
with asphalt binders. The SFE components of asphalt results and discussion section.
binders were measured using Wilhelmy plate method
with three probe liquids namely: Distilled water,
glycerol and formamide. The SFE components of two
types of aggregates namely: granite, and limestone
were adopted from the literature (Little and Bhasin
2006). Fig. 1 shows experimental plan.

Fig. 2 Schematic of Wilhelmy Plate Device

 ... (7)

Where, subscript li indicates ith probe liquid and


subscript s refers to the solid surface.

Fig. 1 Experimental Methodology


4.1 SFE of Asphalt Binders Using Wilhelmy Plate
Method
Fig. 2 shows schematic of the Wilhelmy plate
device used in this study. The Wilhelmy plate method
is an indirect method to measure dynamic contact Fig. 3 a) Sample Preparation, b) DCA Test in Progress

INDIAN HIGHWAYS, September 2017 13


Technical Paper

5. RESULTS AND DISCUSSION acidic in nature with γ+ component 4.96 mJ/m2.


5.1 Contact Angle of Asphalt Binders The CRMB 60 asphalt binder had nearly equal
γ+ (2.20 mJ/m2) and γ– (2.68 mJ/m2) components.
The measured dynamic contact angles of VG 30, The total SFE of VG 30, CRMB 60 and PMB 40
PMB 40 and CRMB 60 binders with different were 12.71, 11.00 and 9.05 mJ/m2, respectively,
probe liquids are presented in Fig. 4. It can be seen which is lesser than SFE of water (72.8 mJ/m2),
that the contact angle measured from water were and hence, water may have a high tendency to
highest for PMB 40 binder followed by CRMB 60, replace asphalt binder from aggregate surface.
and VG 30, however, a different trend was observed
for formamide and glycerol. It is important to note 5.3 Surface Free Energy Components of
that the measured contact angle may not give any Aggregates
idea of coating or spreading of asphalt binders on Usually, the SFE of aggregates is measured by USD
aggregates. The measured dynamic contact angles method using different probe vapors like, water,
are used to estimate the SFE components of asphalt n-hexane, and Methyl Propyl Ketone (MPK).
binder using Equation 7. In the present study, the SFE data of two types
of aggregates (limestone and granite) shown in
Table 1, were taken from the literature (Little and
Bhasin 2006). The granite aggregate had higher
γ– component (412.0 mJ/m2) compared limestone
(259.0 mJ/m2) aggregates. Both the aggregates
had negligible γ+ component (0.0 and 2.4 mJ/m2).
Generally the SFE of aggregates is relatively high
compared to asphalt binder.
Table 1 SFE Components of Aggregates
Aggregate Type SFE Components, mJ/m2
γLW γ+ γ– γAB γTotal

Fig. 4 Contact angle of Asphalt Binder Granite 48.8 0.0 412.0 0.0 48.80
Limestone 44.1 2.4 259.0 49.55 93.70
5.2 Surface Free Energy Components of Asphalt
Binders The γ+ and γ– components of aggregates and
asphalt binders have significant influence on
The SFE components of VG 30, PMB 40 and
their adhesion and debonding potential. Since
CRMB 60 asphalt binders were evaluated by
VG 30 asphalt binder had a high basic component
acid-base theory (Oss et al. 1988) and results are
(10.99 mJ/m2), it was expected that it might
presented in Fig. 5.
have a poor bond with granite aggregates which
also had a high base component. Since PMB 40
had high γ+ (acidic) component compared to
VG 30 and CRMB 60, it might create a better
bond with selected aggregates. It is important to
note that SFE components can give a primary idea
on bonding behaviour; however, it is important to
estimate work of adhesion, debonding, and energy
ratio to estimate a rational parameter to quantify
compatibility and moisture sensitivity of aggregate-
asphalt binder system.
5.4 Work of Adhesion
Fig. 5 SFE Components of Asphalt Binders
The work of adhesion indicates bonding between
The VG 30 asphalt binder was basic in nature aggregate and asphalt binder in dry state. A
with γ– component 10.99 mJ/m2 and PMB 40 was higher work of adhesion shows a good bond and

14 INDIAN HIGHWAYS, September 2017


Technical Paper

vice versa. The Fig. 6 presents work of adhesion showed lower work of debonding with selected
between aggregates (limestone and granite) asphalt binders compared to granite aggregate,
and different types of asphalt binders (VG 30, indicating that limestone aggregate can provide
PMB 40, and CRMB 60). The PMB 40 provided the good moisture resistance. It can be noted that
highest work of adhesion followed by CRMB 60 work of adhesion showed granite as a stronger
and VG 30 for both type of aggregates. The results aggregates, however, this can be considered as
show that granite aggregate can have a better bond bond in a dry state of aggregate-asphalt binder
with PMB 40 and CRMB 60 asphalt binder except
system. The work of debonding shows energy in
VG 30, compared to those of limestone aggregate.
presence of water.

Fig. 6 Work of Adhesion Between Aggregates


and Asphalt Binders
Fig. 7 Work of Debonding for Aggregate-Asphalt
5.5 Work of Debonding
Binder System
The work of debonding indicates decrease in the SFE
of aggregate-asphalt system in presence of water. 5.6 Energy Ratio (ER)
A higher absolute value of work of debonding for a Since work of adhesion and work of debonding
mix shows more sensitive to moisture damage and alone may be used to estimate moisture damage
vice versa. Fig. 7 presents work of debonding for potential of asphalt mixes (Tian et al. 2013),
combination of aggregate-asphalt binder system. researchers have suggested to estimate a rational
It can be observed that PMB 40 provided lower parameter, Energy Ratio (ER) to consider both
magnitude of work of debonding followed by the parameters (work of adhesion and work
CRMB 60 and VG 30 for both type of aggregates. of debonding together). A higher value of ER
The results show PMB 40 provides good moisture indicates a better moisture resistant mix and vice
resistance followed by CRMB 60 and VG 30 with versa (Bhasin et al 2006). Table 2 summarizes
the selected aggregates. ER for different combinations of asphalt binder
While comparing work of debonding for both the and aggregate system and Fig. 8 gives a graphical
aggregates, it was found that limestone aggregate comparison.
Table 2 Energy Parameters for different Combination of Aggregate-Asphalt System

Aggregate- Asphalt Binder WAB Energy Ratio Ranking


System (mJ/m2) (mJ/m )2 (ER)
VG 30 - granite 58.64 -133.10 0.25 6
CRMB 60 - granite 94.83 -84.45 0.86 4
PMB 40 - granite 121.19 -56.02 1.84 2
VG 30 - limestone 63.86 -97.75 0.39 5
CRMB 60 - limestone 85.69 -63.45 1.00 3
PMB 40 - limestone 103.85 -43.23 1.98 1

INDIAN HIGHWAYS, September 2017 15


Technical Paper

through laboratory tests and may also be correlated


with field performance of a pavement.
6. CONCLUSIONS
The present study evaluated moisture sensitivity
of three types of asphalt binders (VG 30, CRMB 60
and PMB 40) with two types of aggregates
(limestone and granite) based on surface free
energy approach. The following conclusions can
be drawn based on the results and discussion
presented above.
1) The surface chemistry of binders can be mea-
sured using SFE method. The results showed
Fig. 8 Energy Ratio for Different Combination of that VG 30 asphalt binder was basic in nature
Aggregate-Asphalt while PMB 40 was acidic in nature.
2) The granite aggregate had higher basic
The ER for limestone aggregate with VG 30,
component compared limestone aggregate. The
CRMB 60 and PMB 40 was found to be 0.39, 1.00
SFE of aggregates is relatively high compared
and 1.98, respectively (Table 2), indicating that to asphalt binder.
limestone aggregate may exhibit a better bonding
3) The work of adhesion indicates that in dry
with PMB 40, followed by CRMB 60 and VG 30.
state, granite can have a stronger bond, how-
Similarly, for granite aggregates, ER was found
ever, it may lose strength in presence of wa-
to be 0.25, 0.86 and 1.84 for VG 30, CRMB 60
ter, and in such situation limestone aggregate
and PMB 40, respectively, showing a strong bond
exhibited a better moisture resistant. Thus, the
of granite aggregates with PMB 40 followed by
work of adhesion and work of debonding alone
CRMB 60 and VG 30 asphalt binder. Overall, order may not indicate a ranking of the aggregate-
of bond between aggregate-asphalt binder systems asphalt binder system and hence it is always
was found to be highest for polymer modified advisable to estimate energy ratio.
binder, PMB 40 asphalt binder, and it was lowest
4) The ER shows that PMB 40 provides better
for unmodified binder, VG 30. A similar thought
bond with limestone and granite aggregate
was drawn based on individual components of the
followed by CRMB 60 and VG 30 asphalt
SFE for aggregates and asphalt binders. The result
binders.
shows that highly basic granite aggregate may
5) The ER ratio indicates that limestone
make a poor bond with basic binder (VG 30). The
aggregate can gives a better bond with all types
limestone aggregate showed a better bond with all
of asphalt binders compared with granite ag-
types of asphalt binders compared to the granite
gregate. The PMB 40- limestone aggregate was
aggregate. Based on ER, the ranking of aggregate-
found to be the highest rank (least moisture
asphalt binder system was found to be as follows:
sensitivity), while VG 30- granite was lowest
PMB 40-limestone > PMB 40-granite > CRMB 60-
in rank (high moisture sensitivity).
limestone > CRMB 60-granite > VG 30-limestone
The study is based on the limited dataset, and
> VG 30-granite. Overall, PMB4 40- limestone
it is recommended that the results presented
aggregate was found to be the highest rank (least
herein be validated through laboratory tests
moisture sensitivity), while VG 30- granite was
and through field performance of a pavement.
lowest in rank (high moisture sensitivity).
REFERENCES
It can be concluded that surface chemistry of
1. Arabani, M., and Hamedi. H., (2011) “Using
aggregate and asphalt binder can have a significant the Surface Free Energy Method to Evaluate the
impact on their bonding potential. The value of Effects of Polymeric Aggregate Treatment on
ER ratio may provide a good input to ensure a Moisture Damage in Hot Mix Asphalt”. Journal
moisture resistant pavement. It is recommended of Materials in Civil Engineering, ASCE, Vol. 23,
that the results presented in this study be validated No. 6, pp. 802-818.

16 INDIAN HIGHWAYS, September 2017


Technical Paper

2. Arabani, M., Roshani. H., and Hamedi. H., (2012) Energy Method”. Airfield and Highway Pavement
“Estimating Moisture Sensitivity of Warm Mix 2013: pp. 54-63.
Asphalt Modified with Zycosoil as an Antistrip 7. Ghabchi. R., Singh. D., Zaman. M, Tian. Q. (2013)
Agent Using Surface Free Energy Method”. “Mechanistic evaluation of the effect of WMA
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Universal Sorption Device", Journal of
"Bitumen Surface Energy Characterization using
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235-272. S. Trepanier. (2014) “Effects of Various Asphalt
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the Asphalt- Aggregate System to Predict Moisture FHWA-ICT-14-004, ISSN: 0197-9191 Illinois
Damage Potential”. Journal of the Association of Center for Transportation, Urbana, IL 61801.
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pp. 59-88. “Chemical and Mechanical Processes of Mois-
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“Laboratory Study of Warm Mix Asphalt for Moisture Sensitivity of Asphalt Pavements A
Moisture Damage Potential Using Surface Free National Seminar, San Diego, California.

IRC TECHNICAL COMMITTEE MEETINGS SCHEDULE FOR SEPTEMBER, 2017


DATE DAY TIME VENUE NAME OF COMMITTEE MEETING
01-09-17 11.00 AM Maintenance and Rehabilitation Committee(B-8)
Fri IRC, R.K.P
01-09-17 10.30 AM Loads and Stresses Committee(B-2)
08-09-17 Fri 11.00 AM IRC, R.K.P Formwork and Temporary Structures Committee(B-7)
Foundation, Sub-Structure, Protective Works and Masonry
09-09-17
Sat 11.00 AM IRC, R.K.P Structures Committee(B-3)
09-09-17 Rigid Pavement Committee (H-3)
09-09-17 Sat 2.30 PM Composite Pavement Committee (H-9)
13-09-17 Wed 10.00 AM IRC, R.K.P Sub-Group B-9.3
15-09-17 10.30 AM Loads and Stresses Committee (B-2)
Fri IRC, R.K.P
15-09-17 03.00 PM Bearings, Joints and Appurtenances Committee (B-6)
16-09-17 10.30 AM Bearings, Joints and Appurtenances Committee (B-6)
Sat IRC, R.K.P
16-09-17 02.30 PM Loads and Stresses Committee(B-2)
22-09-17 11.00 AM Steel and Composite Structures Committee (B-5)
Fri IRC, R.K.P
22-09-17 10.30 AM Loads and Stresses Committee (B-2)
23-09-17 Sat 10.30 AM IRC, R.K.P Urban Roads, Streets and Transport Committee(H-8)
General Design Features (Bridges and Grade Separated
25-09-17 Mon 03.00 IRC, R.K.P
Structures Committee (B-1)

INDIAN HIGHWAYS, September 2017 17