Sixth Lesson

Surface properties

TREATMENT BY SPECIFIC FLUORNATED COMPONDS ON TEXTILES, FIBER, LEATHER, PAPER, AND OTHERS GIVES ADDED VALUES OF WATER AND OIL REPELLENCY, STAIN RESISTANCE, AND

SOIL RELEASE ABILITY

• The surface tension of the perfluoroalkyl group [Rf group : -(CF2CF2)nCF3] is the lowest of all solids on the earth

SURFACE TENSION

n-PerfluoroheptanePFC-HC co-polymers

PFOS PERFLUOROOCTANE SULFONATE

Potassium salt

Acid or amide

USI DEI DERIVATI DEL PFOSIn

divi

duar

e nu

ovi p

rodo

tti e

nuo

ve m

etod

olog

ie

PFOS AS ENVARIONMENTAL RISK

Data extracted from the Swedish Chemical

Inspectorate (Keml) and EPA Dossier August 2004

LABILE COATING Via PFOS

F

SO2N

H2

F

SO2N

H2

F

SO2N

H2

FSO

2NH

2

F

SO2N

H2

F

SO2N

H2

H2OH2O

H2OH2O

Legame fisico deboleTessuto da trattare

Idrorepellenza temporanea

Trattamenti superficiali a base

di prodotti fluorurati:

Nuove opportunità

Surface Tension

TENSIONE SUPERFICIALE

• Perfluoroalkyl chains give water and oil repellency and soil release ability• Alkyl acrylate chains give the ability to form a film and maintain softness • Vinyl chloride and crosslinking monomer gives durability.

FLUORINATED COPOLYMER AS FABRIC COMPONENTS

• Treatment with Fluoropolymers: perfluoroalkyl groups [Rf group: -(CF2CF2)nCF3] cover the surface of the fiber

FLUORINATION OF FIBERS SURFACE

BOTH OF TREATMENTS WITH SILICONE AND FLUOROPOLYMERS CAN REPELLE WATER AND SAUCE, BUT ONLY TREATMENT WITH FLUOROPOLYMERS CAN COMPLETELY REPELLE OIL

FLUOROPOLYMER’ S SURFACE TENSION (10MN/M) IS LOWER THAN THAT OF OIL (20MN/M), ENABLING IT TO REPELL OIL

AFTER TREATMENT WITH SR AGENT, THE CLOTH IS OIL STAIN RESISTANT. IF STAINED, ORDINARY WASHING PROCEDURE WILL REMOVE THE STAIN COMPLETELY

BEFORE WASHING, PERFLUOROALKYL GROUPS [RF GROUP : -(CF2CF2)NCF3] ORIENT TO THE SURFACE AND REPELLE OIL STAINS. AND DURING WASHING, RF GROUP AND HYDROPHILIC GROUPS CHANGE PLACES(FLIP-FLOP), MAKING IT EASY TO RELEASE OIL STAINS

Trattamenti superficiali a base

di prodotti fluorurati:

Nuove opportunità

• In order to engineer a barrier fabric to meet the changing needs, three areas were addressed:

1. Selection of a hydrophobic fiber.

2. Construction of a fabric with a small pore size.

3. Use of chemical finishes to enhance barrierperformance.

Engineering Fabrics with Improved Barrier Properties

COSTRUIRE UN TESSUTO CARATTERIZZATO DA MIGLIORATE PROPRIETÀ BARRIERA

Chemical Finishes

•Today almost all “standard” performance surgical fabrics (disposable and reusable) use fluorochemical finishes to impart higher levels of repellency.

•Without fluorochemicals, these filament polyester fabrics would only have about 1/3 of their barrier properties.

TRATTAMENTI SUPERFICIALI DI FINITURA

Coated/Laminated Surgical Fabric

COATED / LAMINATED FABRIC

H2O liq.

H2O vap.

Microfiber Surgical Fabric

MICROFIBER FABRIC

Impact Penetration Test

Impact Penetration Test

• The impact penetration test is used to determine the penetration of liquids upon impact (e.g., splash by a liquid during a surgical procedure). In this test, an AATCC Impact Penetration Tester is used with blotter paper. The blotter paper is weighed on an analytical balance and placed under the surface of sample of clothing material. The sample is sprayed on its outside surface with 500 mL of liquid from a height of 61 cm. The blotter paper is then reweighed after exposure to liquid impact. The increase in weight is reported as the impact resistance.

VALUTARE IL POTERE BARIERA

LABILE COATING Via PFOS

F

SO2N

H2

F

SO2N

H2

F

SO2N

H2

FSO

2NH

2

F

SO2N

H2

F

SO2N

H2

H2OH2O

H2OH2O

Legame fisico deboleTessuto da trattare

Idrorepellenza temporanea

I TELOMERI FLUORURATI SONO UN’ ALTERNATIVA SCELTA DA MOLTI

F F F F F F

COATING IDROLITICAMENTE STABILE

H2OH2O

H2O H2O

Legame Chimico Stabile Tessuto da trattare

Idrorepellenza permanente

Perfluorodiacyl Peroxides

RO

FH2O2 O

O

O

O

RR

NaOH/H2O

Solvent2 +- NaF

FF

FSYNTHESIS

C. Corvaja, A. Famulari, L. Franco, M. Galimberti, P. Metrangolo, W. Navarrini, G. Resnati, M. Sansotera, Chem. Today, 2006, 24, 3, 17-22.

CF2

OO

O

O

CF2

CF2

CF2

CF3

CF3

Perfluorodi-n-butyryl Peroxide50%

CF3

OO

O

O

CF3

CF3F

CF3F

Perfluorodi-iso-butyryl Peroxide70%

CF3

OO

O

O

CF2

CF2

CF3

Perfluorodipropionyl Peroxide30%

Yields

SO

O

O

O

CF3

CF3F

SF

O

O

O

O

F

F

Perfluoro-di-2-sulphonyl-propionyl Peroxide

50%

Electron Paramagnetic ResonanceHyperfine Coupling Constants (Gauss)

3240 3330 3420

Magnetic Field (Gauss)

87,8; 11,4

3200 3300 3400

Magnetic Field (Gauss)

70,2; 19,7

3150 3200 3250 3300 3350 3400 3450 3500

Magnetic Field (Gauss)

86,4; 16,5; 3,3

3150 3200 3250 3300 3350 3400 3450 3500

Magnetic Field (Gauss)

70,8 ; 17,1

CO2RR O

O

O R

O

R O

O

O R

O

.2 + 2F F

FF F

THERMOLYSIS

Fluoropolymer 2010, 13-16 June 2010, Meze, France

Perfluoroalkylation of Aromatic Substrates

G. Resnati, I. Wlassics, M. Sansotera, P. Metrangolo, W. Navarrini, Chem. Today, 2007, 25, 3, 23-25.

OO

O

O

RR Solvent

OH

O

R CO2ArR+ Ar - H ++F

F FF

R

O

O O

O

R R

O

O O

O

R

CO2.2 + 2RF F F F F

Thermolytic Initiation

RO O

RO

ORH

CO2

RO

O

RH

.

+ +

.RF

F

F

FF

F

Electron Transfer Propagation

Carbocation Aromatization

RO

O

RHR

R

O

O H+ + +

FF

F

F

REACTION MECHANISM

64%68%39%

96%(4%)a

69%(31%)a

89%(4%)a

86%97%95%

Yields

ProductAr-H

R

CH3 CH3

R

Cl Cl

R

CF2CF3R =F CF2CF2CF3

R =FCFCF3 R =

2F

a. Yields of benzylic by-products.

The reaction has been confirmed by:- GC-MS analyses;

- 1H-NMR and 19F-NMR analyses.

19th International Symposium on Fluorine Chemistry, Jackson Hole, USA 2009

Perfluoroalkyl radicals are able to link covalently the unsaturated moieties.

O

OH C

OH

C

O

O

COO

C

O

O

C

C

O

O

O

C

O

OH

C

CO

O

O

C

O

O

O

C

OOC C CO O

Perfluoroalkylation of Carbon Black

It is formed by polycyclic structured aggregates with several functional groups at the edge.

Carbon Black

Fluoropolymer 2010, 13-16 June 2010, Meze, France

R

O

O HCO2R

O

O O

O

RR+

F+ +

F FF

Perfluorodiacyl Peroxides

Perfluoropolyether Peroxides

CF2CF2 O CF2CF2O

T O CF2 O CF2CF2O H O CF2 O CF2CF2O O

CF3 C O F C O FCF2

+ + +

AMW 39000; m/n 1.15; v~43

vm n

Tm n v

O T'm n

T

T, T' = , ,

_HFCF2CF2O RFH CF2CF

O

RF

O O

W. Navarrini, M. Sansotera, P. Metrangolo, P. Cavallotti, G. Resnati., PCT WO 2009/019243 A1

Perfluoroalkylation of Carbon Black

Solvent

n

n

R

R

R +F F

F = Perfluoroalkyl chains, Perfluoropolyether chains

CONTACT ANGLE CHARACTERIZATIONPeroxide Treated Carbon

(x 102 mmolsup/m2)Contact Angle

Untreated Carbon Not stable

Perfluorodipropionyl Peroxide

1,6 17°

3,2 80°

8,0 138°

Perfluorodi-iso-butyryl Peroxide

1,6 137°

3,2 139°

8,0 134°

Perfluorodi-n-butyryl Peroxide1,6 56°

3,2 157°Perfluorodi-2fluorosulphonyl-propionyl Peroxide 3,2 31°

Z-Fomblin Peroxide

0,14 140°

0,46 180°

0,86 180°

2 sec 4 sec 6 sec 8 sec

Untreated Carbon

Perfluorodipropionyl Peroxide

Perfluorodi-iso-butyryl Peroxide

Perfluorodi-n-butyryl Peroxide

Z-Fomblin Peroxide

19th International Symposium on Fluorine Chemistry, Jackson Hole, USA 2009

Perfluoroalkylation of Carbon Black

Solvent

n

n

R

R

R +F F

F = Perfluoroalkyl chains, Perfluoropolyether chains

CONTACT ANGLE CHARACTERIZATION

Fluoropolymer 2010, 13-16 June 2010, Meze, France

M. Sansotera, W. Navarrini, G. Resnati, A. Famulari, C.L. Bianchi, P.A. Guarda, Carbon, submitted

HYSTERESIS

ARCA MeasurementsThe difference between the advancing (Adv-CA) and receding (Rec-CA) contact angle values. Range: (8-20 μl)

0

2

4

6

8

10

CA

Hys

tere

sis

(°)

PFPE CF3CF2CF20.46 0.86

Applications of Perfluoroalkylated Carbon

Black in Fuels Cells

Fluoropolymer 2010, 13-16 June 2010, Meze, France

Membrane

Anodic Catalytic Layer

Cathodic Catalytic Layer

Microporous Layer (MPL) and

Gas Diffusion Layer (GDL)

Bipolar plates

Ionomeric MembranesPerfluorosulphonic PolymersThe addition of fluorinated polymers, acting as binders, stabilizes the catalyst particles on the membrane.

Strato macroporoso290-400 ?m

GAS DIFFUSION LAYER

250-400 μm

Strato microporoso10-100 ?m

MICROPOROUS LAYER10-30 μm

Strato catalitico10-50 ?m

CATALYTIC LAYER (CL)5 -10 μm

MPL• Electric contact between GDL and CL• “Barrier” to water produced at cathode GDL• Homogeneous gas diffusion on CL• Water removal from CL• Electric contact between CL and bipolar plate

l

nn

n

i

iiBrii

i

iiA 1lnlnEV

0Cell

Applications of Perfluoroalkylated Carbon

Black in Fuels Cells

Fluoropolymer 2010, 13-16 June 2010, Meze, France

0.5

1.2

Cel

l V

olt

age

(V)

Current Density (mA/cm2) 1000

Theoretical EMF or Ideal Voltage

Activation Polarization(Reaction Rate Loss)Ohmic Polarization(Resistance Loss)

Concentration Polarization(Gas Transport Loss)

Operation VoltageCurve

Generalized Polarization (Kinetic) Loss Equation

Applications of Perfluoroalkylated Carbon

Black in Fuels Cells

Fluoropolymer 2010, 13-16 June 2010, Meze, France

GAS DIFFUSION LAYER (GDL)

Treatment to increase the Hydrophobicity

Typically a PTFE coating5-30%wt

CARBON FIBERTISSUE

PTFE 10%wt

Applications of Perfluoroalkylated Carbon

Black in Fuels Cells

Fluoropolymer 2010, 13-16 June 2010, Meze, France

FUEL CELL TEST

GAS DIFFUSION LAYER (GDL)

Preliminary Results

Open Circuit Voltage0.94 V

(Good Performance: OCV > 0.9 V)

PFPE 0.24%wt

Covalently Linked to GDL

Synthesis and characterization of environmental friendly fluorosilicone reactive polymeric coatings based on Perfluorinated alkylic chains. These fluorosilicone compounds as a functional material have excellent properties imparted by both fluorine and silicon. Fluoro-silicon coupling agents were found to have high modification ability, in particular: UV-transparency, antireflective films, water and oil repellency on various surfaces.

Wet out cause damp ,clammyfeeling

Water bead off

CA(Water):103±1 deg

CA(Water):42±3 deg

Before treatment

After treatment

7) Perfluorinated alkylic chains fluorosilicone coating

PROJECTS UNDER DEVELOPMENT

Parma - Marzo 2012

Functionalized Carbon Black

Li-Batteries

Applications of Perfluoroalkylated Carbon

Black

Fluoropolymer 2010, 13-16 June 2010, Meze, France

OPVSolar Cells

Plastomeric and Elastomeric Fluoropolymer Fillers SupercapacitorsChromatography