Nanoparticles in Organic Solvents with Polymers · 2017-12-21 · Institute of Mechanical Process...

Institute of Mechanical Process Engineering and Mineral Processing

Nanoparticles in OrganicSolvents with Polymers

Stability and Consequences Upon MaterialSynthesis Through Spray Drying

Martin Rudolph, Urs A. Peuker

German Research Foundationproject: PE1160/7-1

martin.rudolph@mvtat.tu-freiberg.de

June 29th 2011NanoFormulation 2011

Outline

2martin.rudolph@mvtat.tu-freiberg.de

1) Motivation

2) Solution Method

3) Preliminary Investigations

4) Theory of Nanoparticle Interactions

5) Experiments - Stabilitya) Destabilization with non-adsorbing PMMA, PC, PSb) Stabilization with adsorbing PVB

6) Summary and Conclusion

1 Motivation

martin.rudolph@mvtat.tu-freiberg.deJune 29th 2011NanoFormulation 2011

• Synthesis of highly filledpolymer nanoparticle composites ( Nano > 10 %)

Magnetic Beads forsorptive Bioseparation

Hickstein, B., Peuker, U.A.J Appl Poly Sci, 112, 2366

1 Motivation

Composite Micropowderfor Micro Injection

Molding

1 Motivation

• Overcoming problem ofdispersing(deagglomeration + mixing)

1 Motivation

• Overcoming problem ofdispersing(deagglomeration + mixing)

• We present an alternative modular process with thesolution and spray dryingmethod

Outline

1) Motivation

2) Solution Method

8martin.rudolph@mvtat.tu-freiberg.deJune 29th 2011NanoFormulation 2011

• Polymers• Poly(methyl methacrylate)• Poly(vinyl butyral)• Poly(bisphenol A carbonate)

• Nanoparticles• Fe3O4 magnetite,

superparamagnetic

• Solvent(s)• Dichloromethane• Ethyl Acetate

• Surfactants• carboxylic acids (C14 - C18)

PVBPMMA

2 Solution Method

Outline

1) Motivation

2) Solution Method

3 Preliminary Investigations

Investigations with TEM and pc-AFM

• TEM good distribution for spray driedmicrocomposite particle

TEM, spray dried particle

PMMA49 RS21 MAG30

• TEM good distribution for spray driedmicrocomposite particle

• phase contrast AFMshows good distribution in an injection moulded sample

• BUT: both investigations onlyhave a very narrow field of view

phase contrast AFM,injection moulded sample

PMMA64 RS06 MAG30

Rudolph,M. Chem Ing Tech, 82, 2189 (2010)

• phase contrast AFMlarge areas of higher phasevalues

phase contrast AFM,injection moulded sample

PMMA64 RS06 MAG30

Investigations broad field pc-AFM and BSE-SEM

• phase contrast AFMlarge areas of higher phasevalues

• similar „clusters“ for BSE-SEM

back scattering electronSEM, sample as before

PMMA64 RS06 MAG30

Agglomerates? / Primary Particles?

PMMA61 – RS09 – MAG30PMMA61 – RS09 – MAG30 PMMA40 – RS10 – MAG50PMMA40 – RS10 – MAG50June 29th 2011NanoFormulation 2011

Investigations broad field pc-AFM and BSE-SEM

PMMA61 – RS09 – MAG30PMMA61 – RS09 – MAG30 PMMA40 – RS10 – MAG50PMMA40 – RS10 – MAG50

Where are they from?Where are they from?

Outline

1) Motivation

2) Solution Method

• strong VAN DER WAALS attractionleads to agglomeration

• stabilization against agglo-meration with surfactants byliquid-liquid phase-transfer

chemisorption andphysic-chemical deaggregation

surfactant of choice: ricinoleic acid

Machunsky, S. Coll & Surf A, 348, 186 (2009)

Gyergyek, S. J Coll Interf Sci, 354, 498 (2011)

4 Theory of Nanoparticle Interactions

AttractionvdW 24ln

1ln222FattyAcid

Repulsion entroprh

rrhTkA

BornRepulsion entropAttractionvdW ninteractio EEEE

Rosensweig,R.E. A.I.Ch.E.Symp.Ser., 5, 104 (1965)June 29th 2011NanoFormulation 2011

• stability effects by polymeraddition

stabilizing destabilizing

Depletion interaction – Phase diagrams

Ilett,S.M. PhysRevE, 51, 1344 (1995)June 29th 2011NanoFormulation 2011

Outline

1) Motivation

2) Solution Method

5 Experiments – stability

• assessment of the massconcentration of primaryparticles wprimary

• centrifugation and determi-nation of the concentration withTGA, Photospectrometer

centrifugationxprimary, supernatant < 40 nm

diluted supernatant after centrifugation,

increasing cPoly

Rudolph,M. J Coll Interf Sci, 357, 292 (2011)June 29th 2011NanoFormulation 2011

Outline

1) Motivation

2) Solution Method

5a Destabilization with non-adsorbing polymers

martin.rudolph@mvtat.tu-freiberg.deP

destabilization: decreasing primaryparticle concentration with increasingpolymer concentrationJune 29th 2011NanoFormulation 2011

F in %80 70 60 50 40 30

cMag = 24.4 g/l

kinetics of coagulation: not rapid fast drying after mixing should reducelarge amount of agglomerates

kinetics measuredwith DLS

Sympatec Nanophox

cMag = 1.2g/lcPoly = 58.9 g/l

kinetics of coagulation: problem ofcomparability to stability investigationdue to very low colloid concentrationJune 29th 2011NanoFormulation 2011

kinetics measuredwith UVVISat 600nm

cMag = 1.2g/lcPoly = 58.9 g/l

• Nano-Fe3O4 dispersionunder microscope withcMag = 1.5 g/l

• addition of PMMA leadsto larger light-opticallyvisible agglomerates,

= 15 min

• Nano-Fe3O4 dispersionunder microscope withcMag = 1.5 g/l

• addition of PMMA leadsto larger light-opticallyvisible agglomerates

• inverted BSE-SEM ofspray dried particlesPMMA64-RS06-MAG30show agglomerates aswell

• similar agglomeratesizes for dispersion andmoulded BSE-SEM crossection

Outline

1) Motivation

2) Solution Method

5b Stabilization with adsorbing polymer

stabilization: increasing primary particleconcentration with increasing polymer concentration

PMMA, PC

F in %80 70 60 50 40 30

particle size: increase in particle sizewith adsorbing polymer layer forming, of Langmuir type (line)

PMMA, PC

F in %80 70 60 50 40 30

adsorption isotherm: Langmuir type adsorption of PVB on sterically stabilized nanomagnetite

PMMA, PC

04.0/497.0

PVBmax,

PolyPVBmax,

F in %80 70 60 50 40 30

Outline

1) Motivation

2) Solution Method

Solution and spray drying process issuitable for nanocomposite synthesis

HOWEVER: nanoparticle interactionshave to be considered

Added, solved polymers will influencenanoparticle interaction

Stabilization through adsorbingpolymers reveals suitability of thesolution method

6 Summary and Conclusion

AJune 29th 2011NanoFormulation 2011

Institute of Mechanical Process Engineering and Mineral Processing

Thanks for yourinterest!

Sponsored by theGerman Research Foundation:

DFG (PE1160/7-1)

Martin Rudolph

Meet me at poster D-PO3-20» Nanofix – Nanoparticle-wax-formulationsas Additives for Extruder Compounding«

Supplemental

Filler Homogeneity – SEM Analysis (F = 30 %)

cov(A) = 0.98

cov(A) = 5.45

B-SEMcross section Binary Voronoi

coefficient ofvariance - cov

Supplemental

PMMA61 – RS09 – MAG30PMMA61 – RS09 – MAG30

PMMA49 – RS21 – MAG30PMMA49 – RS21 – MAG30

Phase contrast AFM analysis

Rudolph,M. CIT, 82, 2189 (2010)June 29th 2011NanoFormulation 2011

Supplemental

Phase contrast AFM analysis

Supplemental

D – surfactant (detergent) ratio

F – filler concentration

• Composition

surfactant

polymersurfactantnano

surfactant

polymer

Poly – polymer concentration

Supplemental

• Interparticle Distance

surfactant

polymer

polymernano

Supplemental

solidsolidDCMPoly 1

Supplemental

• Gravimetric Characterisation with TGA/FTIR

overallMag,w

centriMag,wxStokes = (20 ± 2) nm

characteristic mass-loss

Supplemental

• Segregation Effects with Spray Drying

fraction x50,3 wMagm(600°C-800°C) /

wMagyield

cylinder 8 µm 47.1 % 15.8 % 29.2 %cyclone 5 µm 44.5 % 15.9 % 60.5 %

filter 3 µm 21.5 % 18.7 % 10.3 %

TGA PSDcylinder cyclone filter

Supplemental

• Spray Drying

• Büchi lab scale spray dryerco-current, inert-loop

• x50, composite 4 µm

• up to 100g/h composites

low highviscosity/concentration

Nanoparticles in Organic Solvents with Polymers · 2017-12-21 · Institute of Mechanical Process...

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