High Barrier Solutions For Plastic Containers Using Fluorination Process 6k4722

High Barrier Solutions for Plastic Containers Using Fluorination Process by- Mr. Bhupendra Singh, B.Sc., B.Sc. (Tech), M. Sc. (Tech) Manager Marketing – Bloom Packaging Pvt. Ltd. [email protected]

Introduction High density Polyethylene/Polypropylene granules has been successfully used in rigid containers as an efficient material for packing products from various industries and it has continuously been preferred material for development of new products or in conversion of existing products packed in materials other than plastics. Unlike other materials e.g. metals & glass etc. HDPE has all the conveniences and efficiency in of light weight, low cost, high stress crack resistance, having high drop impact strength, tremendous flexibility in processing/deg, some protection against moisture, solvents and gases. The only area where Polyethylene/Polypropylene has a drawback against metal or glass container is in the products where permeation and scalping is a problem. The products which typically, presently are not packed in HDPE/PP or shouldn’t be packed in HDPE/PP would be chemicals ranging in different fuels, brake fluids, solvents, solvent based formulations, fuel additives, flavors and fragrances to name a few. To overcome this drawback, HDPE / PP rigid containers are treated with Fluorine gas to form High Barrier Fluorinated Plastic Containers. Principle of Fluorination Process: Fluorination of Plastics is basically a surface modification process, which result in the substitution of hydrogen molecules by fluorine molecules, whereby bulk properties of fluorine treated plastic container / article remains unchanged. H H

C

F

F

F

H

F

H

C

F

F

Figure 1: Fluorination Principle The surface fluorination results in change of the surface properties of polymer drastically, while the bulk properties of the polymer remain often unchanged.

Fluorination Process Plastic Container/ Articles

Fluorination Process

Fluorinated Container/ Articles

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1

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1 and 5: Fluorinated Layers 2 and 4: Boundary Transition Layer 3 : Virgin Plastic Layer Figure 2: Section of a Fluorinated Plastic Sheet The section of plastic container from off line fluorination process consists of (1) A fluorinated layer (2) A boundary transition layer (3) Virgin or untreated Plastic layer as shown in figure 2 from surface to inside.

In Fluorination Process the majority of the chemical reactions occur within this transition boundary layer and the majority of the physical and chemical properties such as density, refractive index, and chemical composition etc. of the polymer are mainly only changed within this layer. The layers can be schematically represented as shown below in Figure 3.

Figure 3: Layers of Fluorine on the Plastic Bottle The fluorination changes the characteristics of the polymer in of polarity, cohesive energy density and surface tension. This in turn has a major effect in reducing the wetting, dissolution and diffusion of non-polar solvents relative to the polymer. Theory of Solvent Permeation and Barrier Function The Permeability Coefficients (P), which is a measure of the rate at which a particular solvent migrates through a polymer, is defined as

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P=DxS Where (D = diffusivity Coefficient, S = solubility Coefficient) Consider the case of a solvent stored in a plastic container. The Permeation of the solvent through this container takes place due to the following steps: Permeation in a polymer consists of four steps as given below: 1. Wetting of the surface by the permeating liquid.

2. Dissolution of the solvent into the polymer.

3. Diffusion of Solvent through polymer and

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4. De-sorption / Evaporation of the liquid through the polymer.

Hence the permeability rate of liquids through polymeric substrate / container is a function of various parameters. The fluorination changes the characteristics of the polymer in of polarity, cohesive energy density and surface tension. This in turn has a major effect in reducing the wetting, dissolution and diffusion of non-polar solvents relative to the polymer as shown in figure 4.

Figure 4: Cross-Section of fluorinated container wall showing the surface treatment. Thus, fluorination is effective in minimizing the permeability of non polar solvents through a polymer surface. Since fluorination modifies only those polymer molecules near the surface, there is no measurable change in the mechanical properties such as tensile strength and impact resistance.

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TESTING Measurements of Fluorination Level: Fluorination treatment is quantified using Fourier Transformation Infra Red Spectroscopy (FTIR). C-H bond shows peak absorption at 1440 – 1480 cm-1, while C-F bond gives peak absorbance at 930 – 1320 cm-1. The FTIR of untreated Polyethylene (PE) is as shown in Figure 5.

C-H Peak

Figure 5: The FTIR of untreated Polyethylene (PE)

As seen in Figure 5, FTIR of untreated PE shows peak for C-H bond at 1440 – 1480 cm-1, while the peak at 930 – 1320 cm-1 for the C-F bond is absent. When Polyethylene is treated with Fluorine by direct offline Fluorination process it shows one more peak at 930 – 1320 cm-1 for the C-F bond as shown in the figure 6.

C-H Peak

C-F Peak

Figure 6: FTIR of treated Polyethylene.

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The level of fluorination is decided based upon its % transmission ratio, which is a ratio of Peak absorbance of C-F bond and Peak absorbance of C-H bond. % Transmission Ratio =

Absorbance of C-F Absorbance of C-H

As the fluorination treatment level is increased, the % Transmission Ratio values also keeps on increasing as shown in Figure 7. Thus fluorination treatment is quantified.

Figure 7: FTIR peaks for increasing treatment levels (U – Represents no treatment, 1-5 represents increasing Level of Fluorination)

It is very difficult to get the same and exact values for the % Transmission Ratio obtained by FTIR every time. Hence a range for these values is taken for the easy under standing of the treatment level. This range of % Transmission Ratio value is than represented in the form of values which is defined as the “Level of Fluorination”. The conversion of range of % Transmission Ratio to Level of Fluorination is as given below in the table I. Transmission Level of Fluorination Ratio (% T) > 12 5 4 > 8 & ≤ 12 3 > 6.5 & ≤ 8 2 > 5.5 & ≤ 6.5 1 > 4 & ≤ 5.5 Table I: The conversion of % Transmission Ratio in to Level of Fluorination.

The fluorinators world wide uses these “Level of Fluorination” which helps their customer as a ready reference during selection of the fluorinated containers. Every product requires different level of fluorination as they require different barrier properties. The customer takes the fluorinated container based on his barrier requirement; more is the barrier requirement or dangerous the chemical the customer goes for higher levels of treatment. 6

There after a customer would test these containers for the product compatibility and stability in the container. After he is satisfied with one level of treatment he will always ask for that level for his particular product package. The level of fluorination is than generally decided by the agreement between the customer and the supplier after the supplier is satisfied that a particular level of fluorination is acceptable for his application. Permeation Testing The solvent permeation through containers is generally tested by an Accelerated Keeping Test (AKT) or as per IS: 2798 which involves high temperature exposure of the filled container over a period of time. Normally, exposure at 500C (+ 10C) for 28 days is considered equivalent to 1 year of normal exposure. After 28 days, a comparison of percent weight loss in the treated and untreated containers will provide an indication of permeation barrier effectiveness. Table II as shown below lists the results of permeation studies performed for various common chemicals. Permeation Test Data for Hydrocarbon-based Solvents (as per AKT test) Untreated Fluorinated Relative Solvent Container Container Barrier % Weight Loss % Weight Loss Barrier Carbon Tetrachloride 28.26 0.05 565 Pentane 98.10 0.21 467 Hexane 61.29 0.19 323 Heptane 24.26 0.08 303 Xylene 42.52 0.21 203 Iso-Octane 4.54 0.03 151 Cyclo-Hexane 22.34 0.15 149 Toluene 61.90 0.52 119 Paraxylene 59.20 0.54 110 1,3,5 Trimethylbenzene 15.85 0.18 88 Benzene 36.68 3.65 10 Chlorobenzene 32.05 5.41 6 1,2 Dichloroethane 11.55 2.89 4 Table II: Effectiveness of Fluorination in reducing the permeability

The data in Table II proves the effectiveness of Fluorination in reducing the permeability of hydrocarbon-based solvents in HDPE containers. The above solvents are commonly used in a majority of industrial, agricultural and household products. It should be noted that combinations of certain chemicals in a specific formulation may cause a reduction in the effectiveness of a fluorinated barrier. Therefore, it is recommended that all formulations be thoroughly tested by the method previously described prior to the final choice of packaging material.

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Permeation Test data of Fluorinated Plastic Containers Table III below gives permeation data for treated and untreated containers when filled with a wide variety of products. As can be observed, Fluorination process reduces the permeation losses to a great extent thereby ensuring close conformation of the product specification at the point and time of use. Permeation Test data for Commercial Products Packaged in HDPE Untreated Container Fluorinated Container (% Weight (% Weight Loss) Loss) Pesticides Cypermethrin 10% EC 28.90 0.12 Cypermethrin 25% EC 32.60 0.25 Chlorpyriphos 20% EC 31.44 0.22 Endosulphan 35% EC 26.12 0.15 Malathion 50% EC 23.99 0.26 Fenvalerate 20% EC 30.66 0.24 Cyflutherin EC 24.23 0.22 Lambda Cyhalothion 5%EC 22.14 0.12 Dicofol 18.5% EC 21.04 0.00 Oxflurofin 23.5% EC 27.98 0.13 Dinocap 48% EC 26.56 0.17 Quinalphos 25% EC 32.96 0.11 Ethion 50% EC 30.01 0.12 Deltamethrin 28% EC 29.11 0.14 Butachlor 50% EC 26.13 0.19 Alachlor 50% EC 27.34 0.15 Triallate 50% EC 29.66 0.13 Monocrotophos 36%SL 20.45 0.00 Paint-Related Products Lacquer Thinner 16.50 3.80 Mineral Spirits 15.07 0.12 Varnish 6.78 0.01 Turpentine 3.92 0.00 Automotive-Related Products Engine Cleaner 2.30 0.00 2-Stroke Plus Motor Oil 7.10 0.44 Table III : Permeation data for treated and untreated containers when filled with a wide variety of products.

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Advantages of Fluorinated Plastic Containers • • • • • • • • • • • • • •

Excellent solvent and moisture resistance Wide range of aggressive chemicals can be packed Cost efficient as compared to tin and aluminum containers Superior strength and durability Greater versatility in container design Better Environmental Stress Crack Resistance (ESCR) Lighter weight Easy Stackability Easy reprocessability High barrier fluorinated containers are approved by CIB (Central Insecticide Board) for a number of agrochemicals. Fluorinated High Barrier Containers are approved by FDA for Direct Food Applications. Fluorination results in a great increase of the surface energy and hence substantial increase in adhesion properties, therefore fluorinated plastic articles can be directly printed. Advantages of Fluorination process is that it is completely dry process and plastic articles of any shape can be treated, which makes this process more versatile. Another significant advantage of Fluorination process is reduction in degree of distortion to the container wall, or ing which is secondary effect of permeation. The ing has a detrimental effect on container aesthetics and in turn consumer acceptance, since the container appears damaged and often has an oily surface. The Fluorinated containers exhibit minimum or no ing compared to untreated containers.

Applications of Fluorinated Plastic Containers Currently the most accepted packaging applications of Fluorinated Plastic Containers include insecticides, herbicides, petroleum based products like lube oil, petrol, cleaning solvents, automotive additives, penetrating oil, Degreasers, paint thinners, essential oil and pine oil. In addition to these, a variety of products where problems of permeation, corrosion and ing are observed in post packing period, in all these cases the possible switch over from tin, aluminum or glass to plastic offers other opportunities in of flexibility of shapes, closure systems and printing to the industry. We shall be too pleased to work closely with the industry to find the most cost effective solutions to the current packaging problems. Packaging of Pesticide, Insecticide, Herbicides chemicals Fluorinated Plastic Containers are widely used in packaging of Pesticide, Insecticide and Herbicide Chemicals because of very high compatibility with most of the pesticides or

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insecticides and absence of corrosion. Biologically active chemicals are also packed in modified Fluorinated Plastic Containers. Flavor and Fragrance Applications

Food processors find that providing only the oxygen barrier is not sufficient, as flavor losses may render containers unacceptable. Polyolefin’s materials usually lack in oxygen and flavor barrier properties. While the problem of oxygen barrier may be solved using conventional multilayer containers, the flavor still escape through these containers. Flavors (Food Products) and Fragrances (Non-Food Products) are mixtures of many volatile complex organic compounds, usually present in ppm or even at ppb level; which impart aroma as well as taste to the food product that we eat. Flavor Loss may occur due to three ways: absorption of flavor/ fragrance into the plastic container, due to migration of plastic additives into the product or due to oxidation of the product by ambient oxygen. In such applications fluorinated containers offer excellent flavor barrier for a wide range of flavors. Fluorinated containers are inert and resistant to most of the organic flavor and fragrances, hence are used to pack these chemicals or solvents which otherwise would require metal or glass container. Fluorinated flavor barrier containers are recommended for use in packaging of vegetable, fruit juice, tea, coffee, spices, and syrup flavors etc. which require very high flavor barrier properties. Automotive Fuels and Fuel Additives Fluorinated Plastic Containers are recommended for packaging of Automotive Fuel and Fuel Additives. The loss of the fuel such as Petrol, Diesel and Kerosene is minimum when they are packed in Fluorinated Plastic Containers. This development improves upon present packaging material used for petrochemical products making it safer in handling as well as brings it closer to standards required in delivering stable quality products to its consumers. Automotive Fuel Tank Applications Today the major commercial application of fluorination technology in the developed countries is for the treatment of HDPE automotive fuel tanks. Plastic fuel tanks have following advantages: • Plastic Fuel tanks are typically 40-50 % lighter in weight and are less apt to explode in the event of fire. • These fuel tanks generally have lower production costs and offer greater freedom of design, allowing more efficient utilization of dead space and thus greater fuel capacity. • These fuel tanks meet the US federal & EPA requirements of permeation loss. 10

Packaging of Aromatic and Non Polar Solvents Fluorinated Plastic Containers are widely used world over in the packaging of aromatic and non-polar chemicals. Packaging of Solvent based Adhesives Fluorinated Plastic Containers are very useful for packaging of solvent based adhesives as well as reactive adhesive components. Packaging of Inks, Paints and Thinners Fluorinated Plastic Containers are used in the Inks & Paints industries for the following solvent based applications. • • • • • • • •

Interior / Exterior Wood Coats Varnish Special Coatings Thinners Melamine Finish Industrial Paints Marine – Primers

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Paint Removers Epoxy – Lacquers Paint Additives Thermoplastic / Heat Resistant Paints Acrylic Emulsions Synthetic Enamel Paints

Conclusions: Fluorinated Plastic Containers and components will find various niche applications in the packaging of highly permeative, hazardous and corrosive chemicals. This technology offers great flexibility in of design and creativity to the end s. The recent applications in fuel tank, thinner, Petro-product, Agro, flavor and fragrance market will provide better alternative packaging options to the respective industries. With its unique advantages Fluorination process can be used in various innovative packaging applications.

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About Author & Bloom Packaging Pvt. Ltd. Mr. Bhupendra Singh a Postgraduate in Plastic Technology from UDCT is associated with Bloom Packaging Pvt. Ltd. as Manager Marketing & Business Development and is looking after the development of the High Barrier Fluorination Solutions for various chemicals. Bloom Packaging Pvt. Ltd. has introduced new range of BLOOMSEAL® Fluorinated plastic packages for packaging applications such as Agrochemicals, Pesticides, Insecticides, Paints, Thinners, Inks, Chemical, Pharma, Food, Flavours, Fragrances, Kerosene, Diesel and Petroleum Products, which require very high barrier properties and chemical resistance properties. Bloom has its state of the art manufacturing facility at Daman and Jammu with its marketing and sales office at Mumbai. Address for correspondence: Bloom Packaging Pvt. Ltd. Ready Money Terrace, 167, Dr. A. B. Road, Worli, Mumbai – 400 018 Tel No. : 022-24970561, 32501137, 32501128 Fax No. 022-24938826 Person: Mr. Bhupendra Singh: (Manager Marketing) Email: [email protected] Website: www.bloompackaging.com

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