New bio-based rheological additives for low-temperature process

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1 CRAYVALLAC Additives New bio-based rheological additives for low-temperature process G. Fauquet Düsseldorf, February 2013 European Coatings Conference

Requirements Storage Requirements No sedimentation Good

stability Extrusion Easy to apply by gun or knife

area Not affecting the curing process Not affecting

2 Why choosing the amide technology? Rheological requirements for sealants: Application Requirements Storage Requirements No sedimentation Good long term stability (in presence of catalyst) Viscosity stability Extrusion Easy to apply by gun or knife Non-slumping Must function regardless of application area Not affecting the curing process Not affecting adhesion In-Service Requirements Not affecting mechanical properties Weather ability Cost effective 2

separation Excellent shear-thinning behaviour > Ease of application and ease of extrusion > Excellent workability Pseudo plastic

3 The amide technology: What are the benefits? Suitable for many different technologies (Epoxy, Silicone, hybrid, polysulfide, PU, ) Good body, high structure > No phase separation Excellent shear-thinning behaviour > Ease of application and ease of extrusion > Excellent workability Pseudo plastic behaviour > No slumping > Fast viscosity recovery Good viscosity stability 3D network of fibers Blank Very limited effect on mechanical properties No effect on curing time With Crayvallac SLT 3 No effect on adhesion properties

control Activation time is necessary Highly dependent on processing conditions To develop an

4 The amide technology: What are the constraints? Require heat activation: The standard amides require between 70 C and 100 C Require temperature control Activation time is necessary Highly dependent on processing conditions To develop an amide which is activated at low temperature! CRAYVALLAC SLT Blank While keeping all the benefits of the amide technology compared to the others. 4

5 Bio sourced materials Crayvallac SLT NEW Crayvallac SLX Crayvallac SL Crayvallac MT Crayvallac Anti-settle CVP 0,0 10,0 20,0 30,0 40,0 50,0 60,0 70,0 80,0 90,0 100,0 % Bio Renewable Content The calculation of the bio-sourced content can be made according to different methods. The following one was chosen in order to show the renewable carbon content of each component : 5 100% of our powder additives are bio sourced at more than 90%. Our last generation of amides, Crayvallac SLT, is bio sourced and bio renewable at 98%.

6 Performance Case study in an MS Sealant

Recipe and conditions FORMULATION MS Polymer S203H 14,9 MS Polymer S303H 10 Plasticizer 17,4 Rheological Additive 3,7 CaCO3 Fillers 49,51 TiO2 Pigments 2,5 UV Stabilizer 0,25 Light Stabilizer 0,25

7 Recipe and conditions FORMULATION MS Polymer S203H 14,9 MS Polymer S303H 10 Plasticizer 17,4 Rheological Additive 3,7 CaCO3 Fillers 49,51 TiO2 Pigments 2,5 UV Stabilizer 0,25 Light Stabilizer 0,25 Dehydration Agent 0,74 Adhesion Promoter 0,5 Hardening Catalyst 0, Aim of the study: To compare different amides and different technologies in terms of processing time, ease of use, rheological and mechanical properties. Activation parameters: 2500 RPM during 30 minutes at the required temperature: SLT: 50 C (no need of external heating) SLX: 80 C, SL: 100 C Fumed silicas, PCC: 50 C (no need of external heating) 7

8 Shorter manufacturing time 90,0 80,0 70,0 60,0 Temperature ( C) 50,0 40,0 30,0 20,0 10,0 Sealant Manufacture Comparison between CRAYVALLAC SLT and CRAYVALLAC SLX 0,0 00:00 00:23 00:46 01:09 Time 01:32 01:55 Crayvallac SLX End of Crayvallac SLT End of process Crayvallac SLX: Activation at 80 C is needed, with a relatively high shear. Then a quite long time is needed to cool the sealant below 50 C. Crayvallac SLT: An activation is still needed at 50 C which means that external heating is not necessary. Then the packaging step can occur almost immediately without cooling. With Crayvallac SLT, the activation is carried out at the same temperature and in the same time frame as fumed silicas. 8

9 Rheological results, viscosity measurements Log Viscosity (mpa.s) Imapct of different additives on viscosity Shear rate (RPM) The additives are added at 3.7%. The viscosity described is at day 3 after production. Since Crayvallac SLT provides the highest viscosity, the addition level can be reduced to reach the same performance as the other products (SL, PCC, fumed silicas) SLT The tested additives exhibit a similar shear thinning behaviour. The Crayvallac SLT shows the highest viscosity. The level of Fumed silicas need to be increased to reach the same results as amides. PCC show very low viscosity mainly due to the fact that the addition level is too low (should be tested at a concentration >20%).

Rheological results, storage stability 1400000 1200000 1000000 viscosity(bf, 5RPM) 800000 600000 400000 200000 0 viscosity compared to viscosity stability of different additives.

10 Rheological results, storage stability viscosity(bf, 5RPM) viscosity compared to viscosity stability of different additives. resul ts The additives are added at 3.7%. The viscosity stability is measured after 15 days at 50 C. The SLT exhibits its full performance just after the production. The stability of the viscosity is also important to be sure that the activation takes place during the process and not during the storage. SLT and SLX show a very good stability. SL and fumed silicas show a lower viscosity stability. PCC is still very low for the same reason as before. 10

11 Limits of the cold process 2,00E+06 1,80E+06 1,60E+06 1,40E+06 1,20E+06 Viscosity (mpa.s) 1,00E+06 8,00E+05 6,00E+05 4,00E+05 2,00E+05 0,00E+00 Crayvallac SLT: Influence of the activation 900,0 temperature for activation time of ,0 mins. 50 C 40 C 30 C Activation temperature 700,0 600,0 500,0 400,0 300,0 200,0 100,0 0,0 Gunnability (g/min) 1 RPM The Crayvallac SLT is added at 3.7%. The viscosity and gunnability are measured at day 3. Conditions are pressure: 2bars, nozzle diameter: 5mm. The idea here is to compare the activation of the SLT at different temperatures. Viscosities and Gunnabilities reached for 40 C and 50 C are quite close. Obtained results reached for 30 C are lower, which means that the SLT is not fully activated after 15 min at this temperature. Only 15 to 30 min of activation are needed to reach full performance at 50 C. Longer dispersion time is still needed at 30 C. 11

12 Performance Case study in a 2K Epoxy sealant

Recipe and conditions FORMULATION Epoxy resin CaCO3 Fillers Rheological Additive 65.8 31.2 3 Total 100 Activation parameters: 2500 RPM, during 30 minutes, at two different temperatures: 55 C and 80 C.

13 Recipe and conditions FORMULATION Epoxy resin CaCO3 Fillers Rheological Additive Total 100 Activation parameters: 2500 RPM, during 30 minutes, at two different temperatures: 55 C and 80 C. Aim of the study: To compare different amides and different technologies in a very simple 2K Epoxy (part A) formula in terms of viscosity results, shear thinning behaviour, nonslumping properties and activation conditions. The different tested additives are Crayvallac MT, SLX, SLT and fumed silicas. Two temperatures were tried to find the optimum activation for the different tested amides. 13

Viscosity results Fumed silicas and Crayvallac MT are similar and give quite a poor shear thinning beahviour Crayvallac SLT exhibits the best compromise between viscosity build up and shear thinning

14 Viscosity results Fumed silicas and Crayvallac MT are similar and give quite a poor shear thinning beahviour Crayvallac SLT exhibits the best compromise between viscosity build up and shear thinning behaviour The described viscosity is at day 3 after production. Viscosity for the blank is mpa.s Crayvallac SLT is more effective than the other additives allowing to reduce the level of addition Its very good shear thinning behaviour allows to reach a high viscosity upon storage and then a low viscosity at high shear for ease of application. The level of Fumed silicas needs to be increased to reach the same results as SLX or SLT products. 14

Impact of the activation temperature The described viscosity is at day 3 after production. Viscosity for the blank is 80 000 mpa.

15 Impact of the activation temperature The described viscosity is at day 3 after production. Viscosity for the blank is mpa.s Crayvallac SLT resists to quite high variations of temperature Performances are much higher allowing to use less quantity and to reduce processing temperature Fumed silicas dispersion step is not temperature dependent Crayvallac MT is better activated at 80 C, showing a strong temperature dependency Crayvallac SLX and SLT show very good stability of the viscosity between an activation at 55 C and at 80 C. 15

Slump test results The tested additives exhibit a similar recovery behaviour The viscosity recovery depends on the additive Crayvallac SLT presents a fast recovery with a pseudoplastic behaviour

16 Slump test results The tested additives exhibit a similar recovery behaviour The viscosity recovery depends on the additive Crayvallac SLT presents a fast recovery with a pseudoplastic behaviour Crayvallac MT takes more time to recover On a rheometer, the sample is destructured for 20 s at a shear rate of 20 s -1, then viscosity recovery is measured under oscillations at 1Hz. Crayvallac SLT will allow to improve nonslumping properties of the sealant thanks to its high pseudoplastic effect. The level of Fumed silicas needs to be increased to reach the same results as amides 16

17 Conclusion A wide range of amide additives are now available, offering various solutions: Depending on processing temperatures: from cold to hot process Allowing to reduce cycle times and production costs Providing higher performance, especially the latest generation Used alternatively or in combination with fumed silicas and PCC Suitable for a wide range of systems On top of being environmental friendly, easier to process at lower cost, Crayvallac SLT is also bio-based at more than 98%. It is therefore the perfect rheology modifier to include in new product development for a good future. 17

Calcium Carbonates for Sealants. Redefining Performance. Kalena Stovall, PhD Imerys Carbonates. October 19, 2016

Calcium Carbonates for Sealants. Redefining Performance. Kalena Stovall, PhD Imerys Carbonates. October 19, 2016 Calcium Carbonates for Redefining Performance Kalena Stovall, PhD Imerys Carbonates October 19, 2016 Calcium Carbonates in Caulks and sealants use high levels of calcium carbonate for desired performance