Sr.

Title/Author Objectives Material Used Methodology

No.
1 Rheological & self healing Evaluate effect of MCP on Rejuvenator – ZS-
properties of asphalt binder asphalt rheological 1 (as core
containing microcapsule
(MCP)
properties material)
Urea
Formaldehyde
Hongliang Zhang et. al., PG 58-16 Asphalt binder resin (UF) – as
grade shell material.
Capsule prepared
by In situ
Polymerization

Paper -1

Rheological and self-healing properties of asphalt binder containing microcapsules

(Hongliang Zhang, Yuzan Bai)

Highlights –

Prepared UF MCP and self healing asphalt containing MCP

MCP increase viscosity, high temperature stability and durability of asphalt

MCP improve self healing properties of asphalt

Objective – To prepare and evaluate effect of MCP on asphalt rheological properties

Key Points-

Material Used- Urea Formaldehyde (UF) SHMCP, SH = Self-healing, MCP = Microcapsule

prepared by in-situ polymerization.

Test Conducted – Penetration, Softening Point, DSR, BBR.

Why Microcapsule, self healing asphalt concept required ?

Actually cracking is common distress in asphalt pavement. With repetitive action of traffic
loading cracks develop in pavement, with time these micro-cracks continue to expand and
accumulate into macro-cracks observe with naked eyes.

Now if not repaired in time it may effect driving comfort, service life of pavement.

SHAP can detect and repair crack itself upto some extent.
How Self-Healing Occur in pavement -

When micro-crack occur and extend to microcapsules in matrix of material, MCP will
breakdown and repairing agent released to repair the micro-cracks.

Factor governing the self healing of asphalt are – gravity, surface tension, thermal expansion,
amount and viscosity of bitumen, packing density of aggregates in asphalt mixtures.

Durability of roads increases with self healing asphalt application. Use of encapsulated
rejuvenators are currently utilized for self healing efficiency of asphalt.

The idea of encapsulated rejuvenators are to modify the viscosity of bitumen in cracked asphalt
mixture, in order to break the equilibrium that keeps bitumen static and force it to drain into
cracks.

Encapsulated rejuvenators are spherical particles, or capsules contain 70% oil, sunflower added
as an additive. With repeated loading the capsules got damaged, break and release the oil. With
release of oil the viscosity of bitumen reduces locally around the capsules, and it can be easily
flow and drain into cracks.

In the field of polymer science MCP Tech. already has good SH results. Now its emerging in the
highway engineering as well for improvement in the healing ability of asphalt pavement.

Thermal Stability and Mechanical Properties of MCP.

Size of MCP – 2-100.5 um, MCP withstand 200 degree C.

Healing process of cracks in asphalt by (SEM) scanning electron microscopy – shows

asphalt containing MCP has good mechanical properties.

Self-healing ability of asphalt mix could be enhanced with encapsulated rejuvenators.

How to prepare Micro-capsule –

 Synthesis of UF resin pre-polymer – 1:2 UF ratio, 15 gm, 40 gm, NaOH soln added to
beaker for pH adjustment 8-9,
 Emulsification of core material – add 200 ml deionized water, 2 gm emulsifier into
beaker, add ZS-1 rejuvenator in beaker, 1-2 drops of defoamer-n-octanol needed.
 Preparation of self healing MCP – NH4Cl added to pH 3-4, curing agent resorcinol
added, NaOh ADDED FOR Ph 7, BAKE THE PRODUCT IN OVEN .

Microcapsule (MCP Content 0, 1, 2, 3, 4, 5% by weight) – preparation methods, core

material, shell material, property of MCP.
Novelty - The dispersion of MCP in asphalt and anti-aging property, high temperature shear
resistance, low temperature cracking resistance and self-healing ability of MCP modified asphalt
rare.

The SHMCP prepared with repair agent as core by in-situ polymerization method and MCP
properties characterized.

Microcapsule – ZS-1 asphalt rejuvenator as core material, UF selected as shell material,

Test Methods –

Characterization of MCP

 Morphology – SEM, HET -200 electron microscope

 Particle size – Laser particle analyzer used to analyze particle size by diffraction or
scattering of light between particles. BT-2002 Laser particle analyzer.
 Chemical Structure –tableting done by FTIR – 7600 & chemical structure of MCP
obtained
 Distribution of chemical bonds, absorption peaks analyzed to verify chemical bonds ,
whether wall material formed & core completely covered.
 Thermal Stability – HS-TGA-101 Thermo-gravimetric analyzer ! to confirm whether they
can withstand corresponding temperature during construction of asphalt pavement.

Rheological tests for asphalt –

Consistency tests – penetration, softening point, ductility, viscosity at 60, 135 degree C.

Durability test – RTFO

DSR , BBR

Self healing tests for asphalt –

SH Ductility test

SH DSR test
 Paper 2

Self-healing of reflective cracks in asphalt mixtures by the action of encapsulated agents

A. Garcia-Hernandez

Key Highlights –

 Encapsulated oil can close cracks in asphalt mixture

 Capsule release the oil gradually
 Aggregate gradation influences the self-healing properties
 Capsules repairs cracks in asphalt
 Self-healing efficiency of porous and SMA is higher than dense graded asphalt
mixture

Composition of capsules and encapsulation procedure –

Self healing agent – sunflower oil, (density, smoke point, flash point), membrane was
calcium alginate (low toxic and availability)

amount of oil released by the capsules – normalized area under FTIR curve calculated.

Study of the mechanical properties and self-healing ability of asphalt mixture containing calcium-
alginate capsules

Sunflower oil encapsulated in calcium alginate

capsule preparation procedure-

Computer tomography scanning of specimens showed large reduction in cracks around

capsules, after resting 4 days at 20 degree C.

How micro-crack develop – The UV rays, temperature, and moisture contribute binder
ageing, which make binder stiffer with time, and loses flexibility and adhesion. Hence the
binder is not able to support temperature and stress cause microcracks.

Additives are softening agents or rejuvenators that modify the chemical composition of old
binder, rebalancing the proportion of light and heavy elements, lowering the viscosity binder.

Induction energy heating asphalt mix, other tech is incorporation of capsules containing
rejuvenators which breaks & release the content when damage occur in their vicinity.
Fabrication of capsules –

Saturating porous aggregates with rejuvenators and sealing them with shell made of epoxy
resin and cement

Micro-encapsulation of the rejuvenator by in-situ polymerization of UFA, Phenol-HCHO,

Methanol-melamine-HCHO.

Materials used –for fabrication , Limestone aggregates, 40/60 penetration grade.

Sodium alginate, cacl2, epoxy resin, micro-cement -10 micrometer, sunflower oil.
What do we get using asphalt-rejuvenator

Maintain smooth pavement, avoid costly repairs, extend road life by 30-40%.
 TRY TO COVER THE ANSWERES FOR FOLLOWING QUERRIES !!!

Advantages of encapsulation, limitation/challenges (if any)

Encapsulation Technologies

 What materials are used?

 What are their properties because of which they are preferred?
 What is the procedure to use it in asphalt binder/mixtures?
 Which equipment used for encapsulation?

Effect of Encapsulation on binder conventional and rheological properties?

Effect of encapsulation on binder chemical properties?

Effect of encapsulation on mixture properties?

Life cycle assessment, cost analysis, and molecular dynamics simulation?

Self-healing asphalt technology-

In the field of material technology, self-healing tech is new member. Incorporating SHT in road
design process has potential to transform the need of road maintenance by –

 Decreasing the unnecessary premature ageing of asphalt pavements

 Reducing the amount of natural resources used to maintain roads
 Decreasing the traffic disruption during road maintenance/process
 Reducing the CO2 emission
 Increasing the road safety, reducing the road accident (death in India due to potholes)
 Cost saving, delay in maintenance operation for several years

Three ways for SHT – nanoparticles, induction heating (steel fibers) and rejuvenation
(encapsulation)

Five essential conditions for SH are-

Good compatibility with bitumen, high temperature stability, ability to survive mixing and
construction conditions, healing temperature of -30 to 40 degree C, continues and multi-time
healing capacity.

Binder Healing agent (Rejuvenation) –

During the service life of pavement, volatile component of bitumen evaporate and oxidation may
occur as a result bitumen ages and loses part of viscoelastic properties.
Binder is combination of asphaltenes and maltenes (resin and oils). Asphaltenes are more viscous
than resins or oils and play major role in asphalt viscosity determination.

Oxidation of aged asphalt during construction and service cause the binder oils to convert to
resin and then resin to asphaltenes, cause age hardening and high viscosity binder.

The viscoelastic state of asphalt mix can be recovered through addition of rejuvenator (cationic
emulsion)

Purpose of rejuvenator is to reduce the stiffness of oxidized asphalt binder and to flux the binder
to extend the pavement life by adjusting the properties of asphalt mix.

By product of waste cooking oil can also be used as binder rejuvenator.

Self assembled monolayers – when crack is in initial phase, it is possible to apply rejuvenator to
wearing course to prevent further crack propagation and pavement failure. Applying rejuvenator
to surface course, life span of asphalt pavement can be extended by several years, applies on top
cm of pavement. One more limitation with these rejuvenators are necessity of road closures for
period of time after application.

To overcome the skid resistance problem due to lower surface friction value microencapsulation
of rejuvenators represent potential means of overcoming this issue.

Microcapsule technique –

Inclusion of rejuvenator into asphalt mix via microcapsule to restore the original properties of
binder, idea is when micro-crack begin to form within the pavement system, they will encounter
capsule within the propagation path, the healing agent will then mix with asphalt binder to seal
up the crack, thus preventing further propagation. This may avoid complete failure of pavement.

Till date most successful microcapsule – Pre-polymer of melamine –formaldehyde modified by

methanol and rejuvenator is oily product.
Capsule size - (since the asphalt mortar film between aggregate particles in asphalt pavement
are found to be 50 um)> than 10 micro meter, & < than 50 micro meter. Size can be controlled
by regulating the core : shell ratio.

Optimum content of capsule must comprise no more than 30 % of overall bitumen volume
within asphalt mix.

Since SHT is new one, demands self assessment of pavement without external intervention –

By development of damage sensing and repair triggering elements

Development of multiple self-healing processes, and development of self-healing mechanism

assessment, cost and environmental benefits of SHT for asphalt pavement design.

Fabrication, characterization and assessment of the capsules containing rejuvenator for

improving self-healing performance asphalt materials: A Review

Asphalt Self-Healing Mechanism, Three Theories are –

 Surface Energy Theory – based on fracture mechanism where decrease of surface energy
is driving force of self-healing behavior.
 Molecular diffusion theory – SH at molecular scale, not reflect the SH of wider cracks.
 Phase field theory - used for microstructure change by AFM, stress level affect the crack
propagation by analyzing AFM results, low stress – no micro crack, medium stress –
crack occur gradually, high stress – micro crack in bee like structure.
 Capillary flow theory – At macroscale, requiring asphalt as Newtonian fluid. Crack
healing model

Enhancement of self-healing efficiency –

 Induction heating method – by adding conductive or microwave absorbing materials

into asphalt & then raising temp. by electromagnetic induction or microwave irradiation
method.
 Limitation of IHM – require human intervention, harmful gases released, aging process
accelerated with elevated temperatures.
 Addition of modifiers such as SBS, nano-materials.
 Rejuvenator encapsulation method – Rejuvenator as core material encapsulated by
shell material to prepare capsule that are mixed with asphalt mixture.
 Limitation of encapsulation – integrity of capsule under thermal and mechanical
condition during asphalt pavement construction, & timely release of rejuvenator once
crack occur during service life of pavement.
 Rejuvenator encapsulation method –
 Absorption Warping method
In situ Polymerization method
Orifice Coagulation bath method

Absorption Waring Method –

Developed by Garcia et al. using porous sand as carrier of core material (traditional rejuvenator
or vegetable oil) and then warping it with hard shell made of cement epoxy resin.

Fabrication process named as absorption wrapping method. Porous sand made of calcium silicate
granules with 1000 of micro-pores to absorb the core material. Capsule size > 1 mm diameter
(determined by particle size of porous sand)

Capsule Type Fabrication Shell Material Structure Encapsulation Diameter

Method Ratio Range
Porous sand AW Porous sand + Sphericity 20.9% 1-10 mm
capsule epoxy + with
cement multinucleate
structure
Microcapsule ISP Melamine Sphericity 85 -95% 1-500 micro-
Formaldehyde with core- meter
(MF), MMF, shell structure
MUF
Ca-alginate Fiber 33-55.64% 100-800
fiber micro-meter
Ca –alginate OCB Calcium 80% 1-5 mm
capsule Alginate Sphericity
Ca-alginate 40% 100 – 500
microcapsule micro-meter

Steps in AWM – saturating porous sand with rejuvenator. (sand will absorb the rejuvenator in
vacuum condition)

Wrapping with epoxy and cement and agitated with cement under action of steel balls. Next the
obtained capsules sieved from cement and cured for several hours. Finally capsules are wrapped
with epoxy and cured again.

In – situ polymerization method –

Su et al. introduced ISP method to the encapsulation of asphalt rejuvenator. MMF shell
microcapsule with average diameter of 5-35 micrometer fabricated by dispersing rejuvenator into
small oil droplets and coating it with hard polymeric shell through polymerization on its surface.

Particle size must be less than 50 micro meter to avoid being squeezed by aggregates, and
chemical reactions at the interface between microcapsule shell and asphalt.
Waste cooking oil, sunflower oil as core material. Later CaCO3 into microcapsule shell, leading
to better thermal stability.

Core-shell ratio, stirring speed of core material adjusted. They concluded microcapsule size – 47
micro-meter, 800 r/min. and 1:1 core/shell ratio shall ratio better morphology SHP.

Steps for Capsule Fabrication in Laboratory –

 Add oily core material rejuvenator into dispersant emulsion and dispersed into oil
droplets using high speed shear emulsifying machine.
 Simultaneously, the interfaces of oil droplets adsorb dispersant molecule whose
hydrophobic groups orient droplets & hydrophilic groups extend out of droplets.
 Soluble prepolymer put into prepared solution and polymerization reaction begins at
interface.
 The molecules of prepolymer gradually deposit on the surface of core particle when []
level reaches certain level., forming inside organic layer of shell.
 For an organic-inorganic composite shell inorganic nano-particle and prepolymer added
together into emulsion after initial prepolymerization of organic shell to form outside
layer of shell.

 Finally filter, wash and dry the prepared capsules.

Limitation – Due to formaldehyde component in the shell they present risk to environment and
human health.

Orifice Coagulation bath method –

Sodium alginate prime material forming capsule shell in OCB Method. It is linear water soluble
polysaccharides extracted from brown sea alginate. It is a copolymer of individual alpha D -
mannur-onic (G) with chemical formula C6H7O6Na.

Preparation of rejuvenator solution and sodium alginate solution, Blending of two prepared
solution to obtain initial Na alginate solution containing rejuvenator. Reaction of Na alginate
with calcium ions by dropping/pumping solution obtained from step 2 to CaCl2 coagulation
solution.

Ca-alginate capsules/fibers were acquired after being washed dried.

Ca – alginate capsule with particle size > 1mm obtained if Na alginate/rejuvenator solution
dropped through orifice into CaCl2 coagulation bath.

Ca-alginate fibers with micrometer scale diameter will be produced if Na-alginate /rejuvenator
solution flows out continuously through needle into CaCl2 bath.

For multiple healing could be obtained using Ca alginate fiber into polymer materials. Ca
alginate shell, Ca –alginate/SiO2 shell and Ca-alginate/grapheme oxide shell.
Ca-alginate capsule –