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Fluorination for High Barrier

Fluorination for High Barrier



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Published by Bhupendra Singh

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Published by: Bhupendra Singh on Nov 06, 2008
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APRIL - MAY, 2008
High density polyethylene/polypropylenegranules have been successfully used in rigidcontainers as an efficient material for packingproducts from various industries and it hasbeen a preferred material of choice fordevelopment of new products or in conversionof existing products packed in materials otherthan plastics. Unlike other materials e.g. metalsand glass etc., HDPE has all the conveniencesand efficiency in terms of light weight, lowcost, high stress crack resistance [ESCR], havinghigh drop impact strength, tremendousflexibility in processing/designing, someprotection against moisture, solvents andgases. The only area where polyethylene/polypropylene has a drawback against metalor glass container is in the products wherepermeation and scalping is a problem. Theproducts which typically, presently are notpacked in HDPE/PP or should not be packedin HDPE/PP would be chemicals ranging indifferent fuels, brake fluids, solvents, solventbased formulations, fuel additives, flavours andfragrances to name a few. To overcome this drawback, HDPE / PPrigid containers are treated with fluorine gasto form High Barrier Fluorinated PlasticContainers.
Principle of Fluorination Process
Fluorination of plastics is basically a surfacemodification process, which result in thesubstitution of hydrogen molecules byfluorine molecules, whereby bulk propertiesof fluorine treated plastic container / articleremains unchanged. The surface fluorination results in changeof the surface properties of polymerdrastically, while the bulk properties of thepolymer remain often unchanged.
Fluorination Process
 The section of plastic container from off line
Fluorinated plastic containers and componentsFluorinated plastic containers and componentsFluorinated plastic containers and componentsFluorinated plastic containers and componentsFluorinated plastic containers and componentswill find various niche applications in thewill find various niche applications in thewill find various niche applications in thewill find various niche applications in thewill find various niche applications in thepackaging of highly permeative, hazardous andpackaging of highly permeative, hazardous andpackaging of highly permeative, hazardous andpackaging of highly permeative, hazardous andpackaging of highly permeative, hazardous andcorrosive chemicals.corrosive chemicals.corrosive chemicals.corrosive chemicals.corrosive chemicals.
Fig. 1: Fluorination PrincipleFig. 2: Schematic Flow diagram of Fluorination Process
High Barrier Solutions
Using Fluorination Process
Bhupendra Singh
Product Manager, BloomPackaging Pvt. Ltd., Mumbai
for Plastic
for Plastic
APRIL - MAY, 2008
fluorination process consists of (1 & 5): Afluorinated layer; (2 & 4): A boundarytransition layer and (3): Virgin or untreatedPlastic layer as shown in Fig. 3 from surfaceto inside.In fluorination process the majority of thechemical reactions occur within this transitionboundary layer and the majority of thephysical and chemical properties such asdensity, refractive index, and chemicalcomposition etc. of the polymer are mainlyonly changed within this layer. The layers canbe schematically represented as shown inFig. 3.
Theory of Solvent Permeation and BarrierFunction
 The Permeability Coefficients (P), which is ameasure of the rate at which a particularsolvent migrates through a polymer, isdefined asP = D x Swhere (D = diffusivity coefficient, S = solubilitycoefficient)Consider the case of a solvent stored in aplastic container. The permeation of thesolvent through this container takes placedue to the four steps as given in fig. 4.Hence the permeability rate of liquidsthrough polymeric substrate / container is afunction of various parameters. The fluorination changes thecharacteristics of the polymer in terms of polarity, cohesive energy density and surfacetension. This in turn has a major effect inreducing the wetting, dissolution anddiffusion of non-polar solvents relative tothe polymer as shown in Fig. 5. Thus, fluorination is effective inminimising the permeability of non polarsolvents through a polymer surface. Sincefluorination modifies only those polymermolecules near the surface, there is nomeasurable change in the mechanicalproperties such as tensile strength and impactresistance.
Measurements of Fluorination Level
Fluorination treatment is quantified usingFourier Transformation Infra RedSpectroscopy (FTIR). C-H bond shows peak absorption at 1440 – 1480 cm
, while C-F bondgives peak absorbance at 930 – 1320 cm
. The FTIR of untreated Polyethylene (PE) is asshown in Fig. 6.As seen in Fig. 6, FTIR of untreated PE showspeak for C-H bond at 1440 – 1480 cm
, while
Fig. 3: Layers of Fluorine on the Plastic Bottle1. Wetting of the surfaceby solvent.2. Dissolution of the solvent into the polymer.3. Diffusion of Solvent through polymer 4. De-sorption / Evaporation of the liquid through the polymer.Fig. 5: Cross-Section of fluorinated container wall showing the surface treatment 
The surfacefluorination results inchange of the surfaceproperties of polymerdrastically, while thebulk properties of thepolymer remain oftenunchanged.
Fig. 4: Permeation in a polymer 
APRIL - MAY, 2008
the peak at 930 – 1320 cm
for the C-F bondis absent. When polyethylene is treated withfluorine by direct offline fluorination process,it shows one more peak at 930 – 1320 cm
forthe C-F bond as shown in the Fig. 7. The levelof fluorination is decided based upon its %transmission ratio, which is a ratio of peak absorbance of C-F bond and peak absorbanceof C-H bond.% Transmission Ratio = Absorbance of C-FAbsorbance of C-HAs the fluorinationtreatment level is increased, the% Transmission Ratio values alsokeeps on increasing as shownin Fig. 8. Thus fluorinationtreatment is quantified.It is very difficult to get thesame and exact values for the% Transmission Ratio obtainedby FTIR every time. Hence arange for these values is takenfor the easy under standing of the treatment level. This rangeof % Transmission Ratio valueis then represented in the formof values which is defined asthe ‘Level of Fluorination’. Theconversion of range of % Transmission Ratio to Level of Fluorination is as given in TableI. The fluorinators world wideuses this ‘Level of Fluorination’which helps their customer as aready reference during selectionof the fluorinated containers.Every product requires differentlevel of fluorination as theyrequire different barrierproperties. The customer takesthe fluorinated container basedon his barrier requirement; moreis the barrier requirement ordangerous the chemical, thecustomer goes for higher levelsof treatment. There after acustomer would test thesecontainers for the productcompatibility and stability in thecontainer. After he is satisfiedwith one level of treatment hewill always ask for that level forhis particular product package. The level of fluorination isthen generally decided by theagreement between thecustomer and the supplier afterthe customer is satisfied that a
Currently the mostaccepted packagingapplications offluorinated plasticcontainers includeinsecticides,herbicides, petroleumbased products likelube oil, petrol,cleaning solvents,automotive additives,penetrating oil,degreasers, paintthinners, essential oiland pine oil.
TransmissionLevel oRatio (% T)Fluorination
> 125> 8 & < 124> 6.5 & < 83> 5.5 & < 6.52> 4 & < 5.51
Table I: The conversion of % TransmissionRatio to Level of Fluorination.
Fig. 6: The FTIR of untreated Polyethylene (PE)Fig. 7: FTIR of treated PolyethyleneFig. 8: FTIR peaks for increasing treatment levels (U – Represents notreatment, 1-5 represents increasing Level of Fluorination)

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