Improved vinyl ester technology for anticorrosion and high performance laminates/grp structures. Stefanie Römhild Paris

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Improved vinyl ester technology for anticorrosion and high performance laminates/grp structures Stefanie Römhild Paris 11.03.2014

DION IMPACT 9133 Premium bisphenol A epoxy based vinyl ester resin designed to give additional benefits in comparison with standard vinyl ester resins Chemically modified to achieve better heat resistance, ie higher HDT than standard vinyl ester resin Chemically modified to be a low foaming system with standard MEKP Impact grade with high reactivity, light color

Standard VE, AVERAGE DION IMPACT 9133 Foaming Mostly yes Strongly reduced HDT 102ºC 112ºC Tensile strength (MPa) Tensile modulus (MPa) Tensile elongation (%) Flexural strength (Mpa) Flexural modulus (MPa) Styrene content (%) 82 80 3300 3350 4-6 4-6 140 135 3300 3400 45 36-39 Comparison DION IMPACT 9133 with standard VE Good chemical resistance, particularly towards acids, some solvents and oxidizing agents Good adhesion to glass, aramide and carbon fibre giving good toughness and fatigue properties Good crack resistance KTW certificate, suitable in contact with drinking water

Reduced styrene emission 24 g/h cm 2 19 g/h cm 2 Styrene emission reduced by 18-20% when comparing DION IMPACT 9133 to standard VE with 45% of styrene

Curing of DION IMPACT 9133 Can be cured with standard MEKP and MEKP recommended for VE, ie Butanox M50 and LPT type, respectively Can be cured using low Colevels Good resin color gives lighter laminates DION IMPACT 9133 Co 1% 0.6% 3% Geltime 23ºC 2% Butanox M 50 20-30 min Standard VE, non Impact grade 2% Butanox LPT 20-30 min DION IMPACT 9133 cured with standard MEKP Standard vinyl ester cured with MEKP recommended for VE lor lower foaming

Flexural strength (MPa), HDT (C) E-modulus (MPa) Post-curing of the DION IMPACT 9133 As known, HDT is function of both curing and post-curing procedures With DION IMPACT 9133, using relatively moderate post-curing temperatures and curing times yields good HDT and mechanical values 160 140 120 100 80 60 40 20 0 7 days at RT 8h at 80C Fully cured Flexural strength (MPa) 92 129 135 HDT ( C) 52 102 114 E-modulus (MPa) 2900 3570 3600 4000 3500 3000 2500 2000 1500 1000 500 0 After 24h at 80 C the resin reaches almost the properties of the fully cured resin (schedule with maximum 120 C) If not post-curing or curing during service can be applied properties are improved using higher level of Co (1-1.5%) and DMA (<1%)

Strength (MPa), HDT E-modulus (MPa) DION IMPACT 9133 and standard VE clear casts cured with Co and Butanox LPT, post-cured at 80 C 120 100 80 60 40 20 0 Mechanical properties at 80 C clear casts DION I Standard DION IMPACT 9133 VE 9133 Flexural strengh (MPa) 81 58 Tensile strength (MPa) 43 28 Tensile elongation (%) 2,9 2,5 HDT 109 92 Flexural modulus (MPa) 2642 2086 Tensile modulus (MPa) 2643 2163 Standard VE 3000 2500 2000 1500 1000 500 0

Strength (MPa), HDT E-modulus (MPa) Properties at 80 C CSM laminate 180 160 140 120 100 80 60 40 20 0 DION IMPACT 9133 Standard VE Flexural strengh (MPa) 171 136 Tensile strength (MPa) 115 84 Tensile elongation (%) 2,3 2 Flexural modulus (MPa) 6282 5345 Tensile modulus (MPa) 6653 5885 7000 6000 5000 4000 3000 2000 1000 0 Laminates post cured at 80 C for 24h. 25-30 wt% glass Benefit of improved heat resistance at operation temperatures around 80 C DION IMPACT 9133 can be used at least 10-15 C higher temperatures 8

DION IMPACT 9133 base resin Product family Non-promoted, non-thixed Filament winding, pultrusion, centrifugal casting, etc applications that require fast & efficient wet-out and good reactivity Chemical resistance applications DION IMPACT 9133-800 Promoted and thixed version of DION IMPACT 9133 Hand-lay-up, spray-up version optimized for large vertical applications, low drain off +2% MEKP geltime 18-30 min DION IMPACT 9133-200 Thixed version of DION IMPACT 9133 Hand-lay-up, spray-up optimized for large vertical applications, low drain off offering the fabricator to adjust geltime after requirements Customised products with adapted viscosity and reactivity based on DION IMPACT 9133 9

Application areas for DION IMPACT 9133 Processes: Filament wining Hand-lay-up Pultrusion and similar processes Centrifugal casting Polymer concrete Protective coatings Application areas: Process equipment, environments requiring excellent chemical resistance Working temperatures in the upper range Applications requiring good mechanical properties

CASE STUDIES DION IMPACT 9133

DION IMPACT 9133 for BFRP Minibars TM ReforceTech BFRP MiniBars, patent pending and produced in a patented process, are short thin reinforcement bars 30-60 mm long. Made of basalt fibre and DION IMPACT 9133 MiniBars directly mixed with the concrete in portions of up to 10% Designed to improve concrete structural strength in conjunction with alkali resistance and bond strength allowing thinner constructions and new freedom in design Application areas: e.g. Submersed concrete, highway slabs, bridge decks, floating infrastructure, agricultural products, etc

Why basalt fibres and DION IMPACT 9133? DION IMPACT 9133 shows optimum reactivity and the high temperature properties required in the production process Combination of the excellent corrosion resistance of the basalt fibres and the DION IMPACT 9133 towards the alkaline environment of the concrete giving a light weight construction material with improved lifetime Higher corrosion resistant to other for metals corrosive environments such as salt and acid environments Marine pipeline Seaweights Outer environment Cl - Cl - Concrete with Minirebars Road environments with high levels of chloride and contamination With permission by Reforcetech Cl - Cl - Cl - Ca + Pore solution K in concrete + OH - Na +

Filament wound GRP pipe DION IMPACT 9133 for filament winding GRP pipe production Project: 1100m pipe line for the cooling system for Geothermal Power plant Working conditions: 65ºC water with max 80ºC Location: Turkey (local project) DION IMPACT 9133 chosen for improved mechanical properties at elevated temperature compared to standard VE Piping project with GRP piping

Pultrusion DION IMPACT 9133 for pultrusion processes Production of pultruded panels intended for use in alkaline environment at elevated temperature DION IMPACT 9133 was chosen due to optimum reactivity and high temperature mechanical properties for pultrusion process and good chemical resistance to alkaline environment

OTHER HIGH PERFORMANCE VE IN THE DION FAMILY

DION 9400/ DION IMPACT 9400 Novolac bisphenol A epoxybased vinyl ester resin HDT 135 C Improved high temperature performance Retains mechanical properties at elevated temperatures Low color and high reactivity for Impact grade Resists organic solvents Good resistance to many oxidising environments An economical alternative to exotic metal alloys Case study Transport tanks for chemical industry Selcotec Norway Various corrosive environments Dion 9400 offers good corrosion resistance to different environments and good mechanical properties

HIGHLY CROSS-LINKED VINYLESTER DION IMPACT 9700 Series Suitable for production of scrubbers and flue gas ducting. Improved glass wet out High HDT of 160 C / 320 F Well suited for hand lay up, filament winding & pultrusion Excellent acid and solvent resistance Very good retention of physical properties at elevated temperatures

BROMINATED BISPHENOL-A EPOXY VE DION FR 9300 Non-promoted, flame retardant vinyl ester resin Class A flame spread with addition of 1.5% antimony trioxide or 3.0% of antimony pentoxide Corrosion resistance similar as Dion 9100 User friendly, 10 min. to 18 hour gel time with excellent cure Extensively used in field fabrication of Chimney and Stack liners 19

ELASTOMER-MODIFIED VINYL ESTER DION 9500 Non-accelerated, rubber modified 9% tensile elongation Good impact resistance Well suited for dynamic loads Low shrinkage Low Peak exotherm Can be used as primer to enhance bonding of composites to dissimilar substrates such as concrete and metals Abrasion 20

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