1st seminar karthik

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Presented By:KARTHIK S.K.

M.Tech (Agril. Engg.)I.D: PALB 3310

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FIRST SEMINAR

Course Teacher

Dr. B Ranganna

Dept. of Agricultural Engineering

3/17/2015 3Dept. of Processing and Food

Engineering

Content

History and Introduction

Nanocomposite and Composite material

Preparation of Polymer Nanocomposite

Classifications of Nanocomposite

Formation and Structural characterization of Nanocomposite

Nanocomposites in Food Packaging

• Clay nanocomposite

• Polymer nanocomposite

• Bio-based nanocomposite

• Starch nanocomposite

• Cellulose nanocomposites

• Protein nanocomposites

Conclusion

References

3

Dept. of Agricultural Engineering3/17/2015 4

• Nanoparticles were used in the glazes on Ming Dynasty (1368-1644)ceramics.

• Carbon black-reinforced rubber: 1900s as a reinforcing agent inautomobile tires

• 1980s: Toyota introduced Nylon - the initial commercial Nanocomposites.

• 1988: Hitachi Metals develops first Nano-magnetic compound,Finemet, used to fabricate low-loss transformers.

• 1998: Inframat LLC patents Nanox 2613 thermal spray, the firstcommercial ceramic Nano composites.

• 2005: U.S. National Academies Keck FUTURES initiative awards grantto Yale/University of Texas team to develop Nano-bio compositesolar cells. (http://www.bccresearch.com)

3/17/2015 5Dept. of Agricultural Engineering


PACKAGING

• Scientific method of enclosing food material/goods in acontainer and it ensure the delivery of goods to theultimate consumer in the best condition indented fortheir use. (Robertson, G.L., 2005)

• Modern packaging has made great advances as resultsof global trends and consumer preferences.

• Nanotechnology can address all these requirementsand extend and implement the principal packagingfunctions – containment, protection and preservation,marketing and communications.

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• Applications of polymer nanotechnology can providenew food packaging materials with improvedmechanical, barrier and antimicrobial properties,together with Nano-sensors for tracing and monitoringthe condition of food during transport and storage.

• The latest innovations in food packaging, usingimproved, active and smart nanotechnology.

• The limits for the development of the new polymernanomaterial's that have the potential to completelytransform the food packaging industry.

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Cont….





“A composite is a combination of two or moredifferent materials that are mixed in an effort toblend the best properties of both.”

A Nano composite is a composite material, inwhich one of the components has at least onedimension that is around 10-9 m.

or

“ A Nano composite is a multiphase solidmaterial where one of the phases has one, two or threedimensions of less than 100 nm, or structure havingNano-scale repeat distance between the differentphases that make up the material”.

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Mechanically the term nanocomposites are

differ from conventional composites due to the

exceptionally high surface to volume ratio of the

reinforcing and/or its exceptionally high aspect ratio.



GENERAL CHARACTERISTICS

Consist of one or more discontinuous phasesof distributed in one continuous phase.

Continuous phase is called “matrix”, whereasdiscontinuous phase is called “filler orreinforcement”.


COMPOSITE MATERIAL

Composite materials are solid ones with multiplephase, which is a combination of two or more materialswith different physical and chemical properties.

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Laminated composites

Fibrous composites

Particulate composites

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Surface to volume ratio


Composite filler ranges and particle size

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Macro Nano

Methods for Preparing

Nanomaterials

Hydrothermal Synthesis

Sol–Gel Synthesis

High-Energy Ball Milling Processes

Microwave Synthesis

Polymerized Complex Method

Chemical Vapour

Deposition



In Situ Intercalative Polymerization

Polymer is formed (initiation of polymerization byheating or radiation or by diffusion) between the layersby swelling the layer hosts within the liquid monomer ormonomer solution.

Melt Intercalation

This method, an environmentally kind one, uses all typesof polymers as well as being compatible with practicingpolymer industrial processes such as injection molding,being the most popular procedure to preparenanocomposites for industrial applications.

In this method, polymers and layered hosts are annealedabove the softening point of the polymer .

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Preparation of Polymer Nanocomposite


Template Synthesis

In situ layered double hydroxide (LDHs) basednanocomposites can be obtained in a template ofpolymer aqueous solution for the formation of host layersand usually employed for water- soluble polymers.

Intercalation of Prepolymer From Solution

The layered host is to be swelled in a solvent (water,toluene, etc.) followed by its mixture with polymer orprepolymer, whereby the chains of the latter intercalatewhile displacing the solvents used for swelling.

Polymer layered nanocomposites results when thesolvent within the interlayer is removed.

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Cont……

Classification of nanocomposites

Nano composites

Polymer based

Non polymer based


Nanocomposites Formation




Structure Characterization

• Nanocomposite structure characterization include particledispersion, changes in the bulk matrix and the nature of theparticle-polymer interface.

• Structure elucidation is the advances in characterizationtechniques.

• Most common techniques used to probe nancompositestructures

– X-ray diffraction (XRD)

– Wide angle (WAXS) and Small angle (SAXS)

– Scanning electron microscopy (SEM)

– Transmission electron microscopy (TEM)

– Infrared spectroscopy (IR) and

– Atomic force microscopy (AFM)

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• TEM determined the polymer structure, void sizeand shape, filler size, shape and distribution, localcrystality and crystal size.

• Polarized light microscopy: accessed the changes inpolymer matrix.

• SEM : assess the structure property relations,especially for toughness.

• The degree of intercalation, exfoliation anddispersion has been traditionally characterized byXRD.

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Cont……


Nanocomposites in Food Packaging

Clay nanocomposite

Polymer nanocomposite

Bio-based nanocomposite

Starch nanocomposite

Cellulose nanocomposites

Protein nanocomposites


• Clay platelets have high surface area(750 m2/g) and high aspect ratio (100 to 200).

• Processing at high shear or sonication techniques arenecessary to de-aggregate or exfoliate the clusters andincrease the surface area exposed to the polymer.

• Clay aggregates must be exfoliated into single plateletsand distributed homogeneously throughout the polymerphase to take full advantage of nanoclays high surfacearea.

• Dispersion of clay layers into the polymer is affected bymismatches between the hydrophobic/hydrophiliccharacter of polymers and clays.

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Clay Nanocomposite


• Polymers are typically hydrophobic and clays arehydrophilic.

• Fatty acid used for chemically modified the clay platelets.Lattice-based thermodynamic model:

• That examines the entropic and enthalpic contributionsduring the formation of a polymer layered-silicatenanocomposite.

• Traditional composite structures contain large quantitiesof filler(apox. 60% vol), but in nanocomposite dramaticchanges in properties are possible at very low loads (<2%vol).

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Cont……


• Exfoliated nanoclays are effective at improving gas barrier properties of polymeric materials.

Cont……


Polymer Nanocomposite

• Polymer nanocomposites (PNC) consistof polymer or copolymer having nanoparticles ornanofillers dispersed in the polymer matrix.

• These may be of different shape (e.g., platelets, fibres,spheroids), but at least one dimension must be in therange of 1–50 nm.

• These PNC's belong to the category of multi-phasesystems (MPS)

• These systems require controlled mixing/compounding,stabilization of the achieved dispersion, orientation ofthe dispersed phase.

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http://en.wikipedia.org/wiki/Polymer

http://en.wikipedia.org/wiki/Copolymer

• Nanocomposites exhibit increased barrier properties,increased mechanical strength and improved heatresistance compared to their neat polymers andconventional composites.

• The use of Nano sized montmorillonite clay to improvemechanical and thermal properties of nylon.

• When used in food packaging, nanocomposite are betterable to withstand the stress of thermal food processing,transportation, storage and also reduce the materialusage.

• Nanoclays montmorillonite (MMT) and kaolinite, carbonnanotubes and graphene Nano sheets are used as particlefiller materials.


Cont……


Characterization of PNC’s

Experimental techniques used for thecharacterization of nanocomposites include

• NMR (Nuclear magnetic resources) for materialsbehaviour: Gives greater insight into the morphology,surface chemistry, and to a very limited extent thequantification of the level of exfoliation in polymernanocomposites

• X-ray diffraction XRD

• Transmission electron microscopy (TEM): Allows aqualitative understanding of the internal structure, spatialdistribution of the various phases, and direct visualizationof defect structure

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• Differential scanning calorimetry (DSC): To understand thenature of crystallization taking place in the matrix.

• FTIR: To detect functional groups and understand thestructure of the nanocomposites

• Dynamic mechanical analysis (DMA): Response of amaterial to oscillatory deformation as a function oftemperature, giving storage modulus corresponds toelastic response to deformation

• Loss modulus: Corresponds to plastic response todeformation.

• Resonance Raman spectroscopy: For structural studies

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Cont……


Biobased Nanocomposite

• Bio polymer include

– plant-derived materials (starch, cellulose otherpolysaccharides, proteins)

– animal products (Proteins, polysaccharides),

– microbial products (Poly hydroxy butyrate) and

– polymers synthesized chemically from naturallyderived

– monomers (poly lactic acid)

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• For packaging applications, biopolymers presentrelatively poor mechanical and barrier propertiesespecially moisture barrier properties due to thehydrophilic nature of biopolymers.

• Biopolymer-layered silicate nanocomposites areimproved physical properties including higher gasbarrier properties, tensile strength and thermalstability.

• Chemically treated nanoscale silicate platesincorporated with appropriate polymers can provideeffective barrier performance against water, gases andgrease.

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Edible coating

Paper boards

Egg trays

Carry bags

Wrapping films

Containers

Application of Biopolymers in food packaging

343/17/2015Dept. of Agricultural Engineering


Starch Nanocomposite

Starch has been extensively investigated as a choicematerial for food packaging applications.

The addition of inorganic materials and synthetic polymershas been proposed to improve water resistance of starch.

Starch-clay : Biodegradable nanocomposite investigated forvarious applications including food packaging.

The young modulus and tensile strength increased with theaddition of MMT clay.

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ZnO - carboxymethylcellulose(CMC) sodiumnanocomposite used as the filler in glycerol plasticized-pea starch.

ZnO-CMC content varied from 0 to 5 wt%, tensilestrength increased form 3.9 to 9.8 MPa, elongation atbreak was reduced form 42.2% to 25.8%, water vapourpermeability decrease significantly.

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Cont……


Cellulose Nanocomposites

• Biopolymer nanocomposite from fruit and vegetablepurees and cellulose nanofibers(CNF) have been recentlystudied as film-forming edible materials.

• Cellulose nanofibers were added to improve tensileproperties, water vapour permeability and glass transitiontemperature of mango puree films.

• Tensile strength increased 4.09 to 8.76 MPa and withincrease in CNF concentration form 0 to 36% and alsoimproves water vapour barrier of the films 2.66 to 1.67g.mm/kPa h m2.

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• Cellulose derivative, hydroxypropyl methyl cellulose (HPMC)to be a promising material for edible coatings or films forpackaging.

• Nanocomposites using chitosan (CS) as nanofiller in HPMC toimprove mechanical and film barrier properties.

• Tensile strength – 30.7 to 66.9 MPa

• Oxygen permeability – 182 to 142 cm3 µ /mm2 d-2 kPa-1.

• HPMC-CS are potential material for food packagingapplications to extent the shelf life of foods.

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Polylactic Acid (PLA) Nanocomposite

PLA has a sustainable, bio-compatible, biodegradable materialwith good mechanical and optical properties.

The large scale use of PLA as packaging material is stillhampered.

Limitation for application of PLA in food packaging is its lowgas barrier properties.

Nanocomposites of amorphous PLA and chemically modifiedkaolinite served good interaction between polymer and clay.

Which led to an increase in oxygen barrier properties of about50%.

The combination of PLA and montmorillonite layered silicatemay result in a nanocomposite with barrier propertiessuitable for food packaging application.

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Protein Nanocomposites

Animal derive proteins

Casein, whey protein, collagen, egg white and fish

myo-fibrillar protein

Plant based proteins

Soybean protein, zein (corn protein) and wheat gluten

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• Compared with non-ionic polysaccharide films, proteinfilms have better oxygen barrier properties and lowerwater vapour permeability due to their more polar natureand more linear.

• Applying nanocomposites technology to improve theproperties of various proteins.


Whey protein

Addition of small amounts (<1 wt%) of

TiO2 nanoparticles significantly increased the tensile properties of WPI film (1.69 to

2.38 MPa.

Soy protein and MMT (hydrogen bond between –

NH and Si-O)

Young’s modulus increases 180.2 to 587.6 MPa with increase in MMT content

from 0 to 20 wt%

Tensile strength of the sheets improves form 8.77 to 15.43 MPa when MMT

content increased from 0% to 16%.

Kaolin based barrier coatings give useful

properties when applied to paper and

paper board.

They are expected to replace

fluorocarbons in extruded polymer

barrier coating

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Soy protein Zein protein

Raw material Advantages Disadvantages

Zein Good film forming

properties

Good tensile and

moisture barrier

properties

Brittle

Chitosan Antimicrobial and

antifungal activity

Good mechanical

properties

Low oxygen and

carbon dioxide

permeability

High water

sensitivity

Advantages And Disadvantages of Protein

Nanocomposite



Raw material Advantages Disadvantages

Whey protein

isolate

Desirable film forming

properties

Good oxygen barrier

low tensile

streangth

high water vapor

permeability

Gluten Low cost

Good oxygen barrier

Good film-forming

properties

High sensitivity to

moisture and brittle

Soy protein

isolate

Excellent film forming

ability

Low cost

Barrier properties

against oxygen permeation

Poor mechanical

properties

High water

sensitivity

Cont……

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Other Applications of Nanocomposite

• Electro catalyst in batteries for energy saving

• Light weight materials for less fuel consumption.

• In artificial joints, economically beneficial

• Carbon nanotubes most widely speaking nanomaterial which can bemade as nanocomposite fibers.

• Abrasion and wear applications

• Marine application

• Food packaging

• Fuel tanks

• Films

• Environmental protection

• Flame ability reaction

• Erosion and corrosion Applications




The application of nanocomposites promises to

expand the use of edible and biodegradable films that

reduce the packaging waste associated with

processed foods that supports the preservation of

fresh foods by extending their shelf life.

Nanocomposites are upcoming materials which

shows the great changes in all the industrial fields and

it is also going to be an economical barrier for

developing countries as a tool of Nanotechnology.

Conclusion

47


AMIT ARORA AND PADUA, G.W., 2010, Review: Nanocomposites in

Food Packaging. Journal of Food Science and Technology, 75 (1): 43 -

49.

HENRIETTE, M.C. DE AZEREDO., 2009, Review: Nanocomposites for

food packaging applications, Food Research International, 42: 1240 –

1253.

AHMED M. YOUSSEF., 2013, Polymer Nanocomposites as a New

Trend for Packaging Applications, Polymer-Plastics Technology and

Engineering, 52: 635 - 660

TANG, X. Z,. KUMAR, P., ALAVI, S..AND SANDEEP, K. P. , 2012,

Recent Advances in Biopolymers and Biopolymer-Based

Nanocomposites for Food Packaging Materials, Critical Reviews in Food

Science and Nutrition, 52: 426 – 442.

References

48


References

3/17/2015 49

ANDREA SORRENTINO, GIULIANA GORRASI AND

VITTORIA VITTORIA, 2007, Potential perspectives of bio-

nanocomposites for food packaging applications, Trends in Food Science

& Technology, 18: 84 – 95.

PAUL, D.R., ROBESON, L.M., 2008, Polymer nanotechnology:

Nanocomposites, Science Direct, 49: 3187–3204.

http://www.bccresearch.com/blog/report-archives/nanocomposites-

overview.html

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