Clay Nanocomposites and Trialkoxysilane Functionalized Quaternary Ammonium Compound For Packaging Applications Yusuf Z. Menceloglu Funda!nceo"lu, Kazım Acatay,!lhan Özen, Why Nanocomposites? Electrical Conductivity Mechanical Properties (Tensile Strength, E-Modulus & Dimensional Stability) Permeability (Gas, water vapor & hydrocarbon) Bio-degradability Advantages of Nanocomposites Thermal Stability (HDT) Surface Appearance Chemical Stability Flame Retardancy
Materials Used in Nanocomposites Barrier Layered structure Ion distribution Catalytic Clay Cation Exchange Capacity (CEC) Exfoliation
ICP Analysis Raw Clay Na% K% Fe% Ca% Mg% Mn (ppm) P (ppm) Re!adiye 1,70 0,73 1,42 2,01 0,79 653 582 Rockwood (Nanofil 116) 2,11 0,18 1,88 1,16 2,46 80 352 CEC Determination (Methylene Blue Test) Re!adiye: 104 meq/100 g Rockwood: 100 meq/100 g 15 N-NMR Analysis Nanocomposite Language P. C. LeBaron, Z. Wang, T. J. Pinnavaia, Polymer-layered silicate nanocomposites: an overview, Applied Clay Science 15, 11 29, (1999)
Mechanism of Oxygen Barrier Improvement 7 Film W 1 clay layer L Aspect ratio: L / W Oxygen molecule Thickness Permeability = Diffusivity*Solubility Chemical compatibility and processing should also be kept in mind!!! Materials PET Molecular structure PET-co-5SIPA PP PP-g-MA
NON POLAR / POLAR Materials RKQR4 RWQR4 SE3010 RKQR1 RWQR1 SE3000 Structure Re!adiye clay modified with etoxylated quaternery ammonium chloride (for PET) Rockwood clay modified with ethoxylated quaternery ammonium chloride(for PET) Commerical Rockwood organoclay modified with dimethyl benzyl stearyl ammonium chloride* (for PET) Re!adiye clay modified with ditallow quaternary ammonium chloride (for PP) Rockwood clay modified with ditallow quaternary ammonium chloride (for PP) Commerical Rockwood organoclay modified with dimethyl distearyl ammonium chloride* (for PP) XRD Analysis 1.2 nm Re!adiye raw Rockwood raw PETRKQR4 85/15 MB PETRKQR4 98/2 Film RKQR4
SEM Analysis Re!adiye raw (RK) RKQR4 PET/RKQR4 98/2 Preparation of the the films Chill roll line Iwamoto biaxial stretcher
Thermal Characterization KONG Y., HAY J.N., Polymer, 43, 14, 3873-3878, (2002) Polyethyleneterephthalate Oxygen Gas Permeability Degree of crystallinity decreases, but OGP decreases as well!!!
Polypropylene Oxygen Gas Permeability Degree of crystallinity increases and OGP decreases Summary Synthesis of thermally stable organoclays Intercalated and partially exfoliated structures commercial and local organoclays Compatibility of clay and polymer matrix is very important both for crystallinity and barier property Degree of crystallinity and homogenous distribution-compatibilities are very important Surface modifications of organoclays improves compatibility as well as barrier property
Trialkoxysilane Functionalized Quaternary Ammonium Compound Functionalization of surfaces by Sol-Gel Approach The most important goals for functional surfaces are: 1. Improved stability against mechanical, chemical, photochemical or thermal destruction, 2. Improved repellency properties against water, oil and soil, 3. Changed light absorption and emission properties from the UV up to the IR region, 4. Improved electric conductivity, e.g., for antistatic and electromagnetic protective effects, 5. Immobilization and controlled-release of active species, e.g., with biocidal, therapeutic and well-being effects. >?%.&/"'+5/* =*5-)+&/$)#2%.&/.'&5'( ;#"'&<%/)2%#*1%(/)2% &'.'22'*+' 6'+&'#('1% )*7#--#5/*!"#!"#$%&#' (&)*+,-.& 8/*"&/22'1%&'2'#('%/9% /)2%#*1%7#0/:&( 4)/+#"#235+%.&/.'&5'(,-.&/0'1%#$&#()/*% ("#$)2)"3!"#$%&'()("#*+'
Functionalized SiO 2 Particles 29 Si NMR 13 C NMR Quarternary Ammonium Compounds as an Antimicrobial agent! Certain long alkyl chain quaternary ammonium compounds are used as antimicrobials and disinfectants.! Also good against fungi, amoeba, and enveloped viruses.! Quats act by disrupting the cell membrane and proteins.! Quats kill just about everything except endospores, Mycobacterium tuberculosis, lipid-containing viruses, and Pseudomonas spp.! Quats are deactivated by soaps, other anionic detergents,! Also, they are not recommended to be used in hard water.! Effective levels are at 200 ppm.! They are effective at temperatures up to 100 ºC.! Along with sodium hypochlorite, quats is one of the primary chemicals used in foodservice industry as a sanitizing agent. http://en.wikipedia.org/wiki/quaternary_ammonium_cation
Grapnel Technology! A highly active microbicide is covalently bonded to a substrate, include synthetic, cellulosic films, webs or fabrics.! No migration to the skin or the environment! Does not allow for the development of adaptative organisms.! No Zone Of Inhibition! The microbicide is bonded.! Does not migrate from the substrate.! Continuous action isn t depleted.! Launderable without loss of efficacy.! is safe for humans and the environment Non Toxic Biodegradable! http://earth1.epa.gov/pesticides/foia/ reviews/107401/107401-33.pdf! Evaluation of the Cytotoxic Efects of Bis-quaternary Ammonium Antimicrobial Reagents on Human Cells-Toxicology in Vitro 14 (2000) 139-147! Similar structure is EPA registerd Quarternary ammonium compounds are readily biodegradable Primary Biodegradation of Amine Oxide and Quaternary Ammonium Amphiphiles Folia Microbiol. 38 (1), 43-48 (1993) Role of Acinetobacter for Biodegradability of Quaternary Ammonium Compounds Bull. Environ. Contam. Toxicol. (2000) 64:764-770 no heavy metals, silver, arsenic, tin, cupper or polychlorinated phenols and no migration in waste water
23 Storage Tests Antimicrobial applied corrugated box and freshly collected tomato samples (free standing and near to side and bottom) Stored at 11 0C 20 days Lesion and appearance after 20 days 24 Lesion diameters on tomatos contact to the surface
samples taken for microorganism counts 25 (A) Sample taken from touched area, (B) sample taken from untaoched area, (C) determination of colonies from touched and untouched samples. Determination of region of lesion after storage Spoiled/Rotten Tomato Ratios 26 % intensity of sick tomato on untouched and touched samples % intensity of spoiled tomato touched on box wall LSD (P"0.05)
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