Glass surface modification by coating deposition Coating of metal oxide and metal (low- emission coatings) Amorphous coatings produced by CVD and sol-gel processes

Glass surface modification Glass coating with metal oxide and metals layers Methods of glass coating: Pyrolytic coating („hard” coatings) Magnetron sputtering („soft” coatings”)

Pyrolytic coating of glass (metal oxide coatings – „hard”) Spraying of surface glass with inorganic and metal-organic compounds; temperature 260oC – 580oC; thermal dissociation of used compounds and formation of metal oxide layers (Co, Ni, Fe,… oxides) Method used to production marked building glass „Antelio” (brownish, silvery, green) Transmittance coefficient of solar energy 37 – 68%.

Magnetron sputtering (metal coatings – „soft”) Cathodes sputtering of metals or their combinations supported by magnetic field Cathodes: Au, Ag, Ti, Cu, Cr, Sn, Ni, InSn, CoCr, NiCr (Solar Control layer)

Magnetron coatings deposition „Soft” coatings – cathode sputtering DC Valve Silver Anode Cathode Vacuum

Magnetron coatings deposition Descripion of process: Dilution and ionization of gas at high voltage and vacuum Cathode bombardment by positive ions (gas atoms ionization) Sputtering of silver ions from the cathode Deposition of Ag on the anode – formation of metal layer

Thickness of both – glass and coating; comparison Coating ~ 35 nm Ag ~ 10 nm Glass ~ 80-90 nm 106 m 4 mm

Sunscreen windows Coloured glasses or glass covered with the reflective solar coatings Glass colour and transparent coefficient depend on the type of used covering Sunscreen windows allow to stop even 90% of solar energy

Sunscreen windows Solar energy transfer through the glass covered and not covered with Solar-Control coating

Glass surface modification electro-float method Ions diffusion to surface layer of glass during float glass production System: cathode (tin Sn) anode (modifier) Due to electric field proper ions pass from modifier into glass surface (colored glass production – „Parsol”) This method is used to produce surface colored widow glasses of various color

Production method of amorphous layer:: Glass surface modification amorphous layers Production method of amorphous layer:: glass-works method (glass on glass); CVD (reactions from gas phase); Sol-gel process;

Glass surface modification Coatings deposited with „glass-ware” method Coating (plaiting) of one glass by other one” for example – colorless glass coated with color one Domestic glassware, plate glass, filtres

Glass surface modification Deposition of coatings using CVD(Chemical Vapour Deposition) method - protective coatings: SiO2, SiO2-TiO2; - coatings of modified properties: SiO2-GeO2; SiO2-Bi2O3;

Amorfous coatings produced by CVD method Starting materials in the form of liquid dosed to plasma burner  Transformation of starting compounds (SiCl4, TiCl4) GeCl4 to vapour state, ) Reaction in the gas phase (hydrolysis or oxidation): SiCl4 + 2H2O SiO2 + 4HCl SiCl4 + O2 SiO2 + 2Cl2 Depostion of gas reaction products (SiO2) on the substrate of lower temperature (vitrification)–amorphous coatings, optical fibres

Glass surface modification Amorphous coatings deposited by the sol-gel process: Inorganic Organic-inorganic (hybrid layer)

Sol-gel process

Sol-gel amorphous coatings Inorganic coatings protective: SiO2, reflective: SiO2-TiO2 colored: SiO2-R2O3 (R –transition metals) fluorescent: SiO2 + rare earths Anty-corrosion (SiO2-ZrO2)

Organic-inorganic coatings WHAT ARE HYBRIDS ? Hybrid material - any organic-inorganic or bio-mineral system in which at least one of the components, organic or inorganic, is present with a size scaling from tenths to tens of nanometers. Components making up the hybrids could be molecules, oligomers or polymers, aggregates and even particles.

CLASSIFICATION OF HYBRIDS (following the nature of chemical bonding between the organic and inorganic species criterion) Class I: Includes hybrids systems where one of the component (organic, biologic or inorganic), which can be molecules, oligomers or polymers is entrapped within a network of the other component. The systems of this kind are essentially based on Van der Walls, hydrogen bonding or electrostatic interactions Class II: Gathers the hybrids materials where the inorganic and organic compopnets are chemically bonded by a covalent or ionic-covalent bonds

ORMOCER®s ORganically MOdified CERamics – inorganic-organic hybrid materials on the molecular scale

STRUCTURE’S ELEMENTS O O R Al., Ti, Zr Si O O O (R) Si O O Si Si O O functional groups (1) O O R heteroatoms in inorganic structures (2) Al., Ti, Zr Si O O O (R) Si organic crosslinking (4) O O inorganic silica network (3) Si Si O O

TYPES OF PRECURSORS OF HYBRID MATERIALS Structural units of inorganic-organic hybrid are connected by strong covalent bonds. The building units of these hybrid polymers base on different types of precursor molecules. These precursors can be classified by their network forming or modifying roles. Basically four different types of precursors can be used for the synthesis of hybrid polymers …

TYPES OF PRECURSORS TYPE 1: inorganic network formers, alkoxides of Si (TMOS, TEOS), Al (Al-tri-sec-butylate), Ti (Ti-isopropylate) and Zr (Zr-butylate); TEOS Si(OC2H5)4 TYPE 2: inorganic network formers with organic non-reactive group; phenyltriethoxysilane (PhTES) [(OC2H5)3Si(C6H5)] TYPE 3: inorganic network formers with reactive organic group for cross linking/polymerization reactions; 3–glycidoksypropyltrimethoxysilane (GPTMS) [(OCH3)3Si(CH2)3OCH2CHOCH] TYPE 4: organic monomers which can react via chemical cross linking or polymerization reactions with modified metal alkoxides;

APLICATIONS … Protective coatings for sensitive surfaces (scratch and abrasion resistance) Increasing chemical resistance (corrosion protection) Barrier layers for gases, solvents, flavors, ions

APLICATIONS … Decorative coatings Antireflective coatings

APLICATIONS … Hydrophilic/-phobic and oleophobic functions (antiadhesive coatings) Antistatic coatings Sensor layers (for gases and ions) Adhesive systems (e.g. for optical fibers) Doped optical coatings for photonics

SOL-GEL PROCESSING SCHEME FOR ORMOCER® COATINGS RnSi(OR’)4-n Si-, Al-, Zr-alkoxides etc. alkoxides water, catalyst hydrolysis + condensation alcohol, water SOL GEL substrate dip- spray- spin- coating wet film temperature, radiation alcohol, water coating