Polysiloxane Coatings

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Polysiloxane Modifications
Dr Adrian F Andrews New Product Development Manager Protective Coatings - Worldwide International Protective Coatings UK
adrian.Andrews@uk.akzonobel.com
 
1. INTRODUCTION
 Aliphatic Acrylic Polyurethanes are often used as the durable Finish Coat in conventional High Performance Coating Systems for the protection of steel. The aesthetics (gloss and colour retention) of the Polyurethane Finish diminish with time on exposure to the environment and is very dependent on the coatings formulation with the best performing products typically being the most expensive. Organic Coatings undergo thermal oxidation, photo-initiated oxidation and chemical attack when exposed to the environment resulting in a degradation of properties, which in Finish Coatings will include gloss and colour loss as well as embrittlement and potential loss of adhesion to the Base Coating. Polysiloxane Coatings on the other hand are much more resistant to these degradation mechanisms due to the nature of the Polysiloxane backbone. The SI—O bond is stronger (452 KJ mol
-1
) than the C—C bond (350 KJ mol
-1
) in Organic Coatings making it more heat and UV resistant and as it is already oxidised Polysiloxanes are resistant to atmospheric oxygen and most oxidising chemicals. Consequently Polysiloxane Coatings are more durable (weatherable) than Polyurethane Coatings and will retain gloss and colour for a much longer period of time. The improvement in durability seen by using Polysiloxane resins can be compromised if the coatings formulation is less than ideal. Other important coatings properties such as flexibility on ageing, hardness, edge protection, tolerance to over-application, external overcoatability, adhesion to Base Coats and product storage stability may also be affected. For example, wrongly formulated Polysiloxane Finish Coatings may embrittle with ageing resulting in cracking and detachment on long-term exposure to the environment. There are now a number of Polysiloxane Finish Products on the market from Coatings Suppliers and Raw Material Suppliers which offer low viscosity, low VOC, non-isocyanate, highly weatherable properties.
 
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2. SUMMARY
This paper will focus on the performance properties obtained from a range of commercially available Polysiloxane Products with particular emphasis on the durability and mechanical properties of the coatings on long-term environmental exposure. Polysiloxane Coatings are organically modified to achieve a balance of film properties (adhesion, flexibility and cost) and are sometimes referred to as Inorganic Organic Hybrid Coatings. This can be achieved by blending organic resins with Polysiloxane resins or organically modifying the Polysiloxane resin itself. The types of organic modification vary and range from acrylated urethanes, hydrogenated epoxies and modified acrylics (with epoxy, hydroxyl, amine and alkoxysilyl functionalities) to modified methyl phenyl polysiloxanes with various functionalities. The level of organic modification necessary depends on the specific system and needs to be experimentally determined. The commercially available Polysiloxane Products analysed suggests the level of organic modification ranges from 20% to 70% w/w (on resin solids).
Table 1: Type of Organic Modifications
Product Organic Modifications Inorganic
Urethane Polysiloxane*(A) Urethane Acrylate Me/Ph Siloxane, Amino silane  Acrylic Polysiloxane (B) Acrylic Me/Ph Siloxane, Amino silane  Acrylic Polysiloxane (C) Acrylic
(t-amine and hydroxy functional)
  Amino silane Epoxy Polysiloxane (D) Hydrogenated Epoxy Me/Ph Siloxane (Amine functional)  Acrylic Epoxy (E) Acrylic Epoxy Me/Ph Siloxane Epoxy Polysiloxane (F) Hydrogenated epoxy Me/Ph Siloxane, Amino silane Epoxy Polysiloxane (G) Hydrogenated epoxy Me/Ph Siloxane? Amino silane? (Datasheet) Epoxy Polysiloxane (H) Hydrogenated epoxy Me/Ph Siloxane, Amino silane (Amine)
* This material is marketed as a “2
nd
 generation acrylic polysiloxane”
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Table 2: Level of Organic Modifications
Product Level of Organic  Modifications Inorganic:Organic (% wt on binder)
Urethane Polysiloxane(A) 61:39  Acrylic Polysiloxane (B) 72:28  Acrylic Polysiloxane (C) 77:23 Epoxy Polysiloxane (D) 55:45  Acrylic Epoxy (E) 37:63 Epoxy Polysiloxane (F) 58:42 Epoxy Polysiloxane (G) ? Epoxy Polysiloxane (H) 60:40
* This material is marketed as a “2
nd
 generation acrylic polysiloxane” Too low a level of organic modifications can result in the coating having too high a Polysiloxane characteristic (glass like) with the potential for cracking and loss of adhesion on prolonged testing. Too high a level of organic modifications will detract from the Polysiloxane properties and may result in compatibility issues.
2.1 Durability
Figure 1 gives an indication from accelerated weathering using QUV-A of the improvement in durability achieved over an aliphatic acrylic polyurethane. An approximate view of effectiveness is to consider the time taken for the coating to lose 50% of its initial gloss.
Figure 1 : Gloss Retention in QUV-A
QUV-A Gloss Retention
020406080100120020004000600080001000012000
Hours Exposure
   G   l  o  s  s   R  e   t  e  n   t   i  o  n   %
Urethane Polysiloxane (A)Acrylic Polysiloxane (B)Epoxy Polysiloxane (C)Polyurethane
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 All but two of the Polysiloxane Products (E and H) show improved durability compared to the aliphatic acrylic polyurethane even at this early stage of testing of the majority of the products. Why the two exceptions are showing only similar performance to the Polyurethane is unknown, although, the high organic content of Polysiloxane (E) could have an effect on durability. Longer term it may well be the Polysiloxanes (E, H) will outperform the Polyurethane – time will tell. Table 3 shows the exterior exposure data for these products in a C4 or C5 (ISO 12944 Classification) environment. It is too early to draw conclusions for the majority of these products but for the Acrylated Urethane (A) and Epoxy (F) modified Polysiloxanes the data (5 years) supports the ranking shown in QUV-A viz the Polysiloxanes significantly outperform Polyurethanes.
Table 3: Gloss Retention External Exposure
% Gloss Retention – External Exposure Location - 5 years Urethane Polysiloxane
*
 (A) Epoxy Polysiloxane (F) Polyurethane
 Australia – Brisbane 82 77 10 – 15 Saudi Arabia 82 78 10 15 USA Houston 90 87 10 15 Singapore 82 76 10 15
* This material is marketed as a “ 2
nd
 generation acrylic polysiloxane”
QUV-A
020406080100120050010001500200025003000
Hours
   G   l  o  s  s   R  e   t  e  n   t   i  o  n   %
Urethane Polysiloxane (A)Acrylic Polysiloxane (B)Acrylic Polysiloxane (C) Epoxy Polysiloxane (D)Acrylic Epoxy Polysiloxane (E)Epoxy Polysiloxane (F)Epoxy Polysiloxane (H)Polyurethane
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