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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 SIO bond is stronger (452 KJ mol-1) than the CC 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, nonisocyanate, highly weatherable properties.

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 Urethane Polysiloxane*(A) Acrylic Polysiloxane (B) Acrylic Polysiloxane (C) Epoxy Polysiloxane Acrylic Epoxy Epoxy Polysiloxane Epoxy Polysiloxane Epoxy Polysiloxane (D) (E) (F) (G) (H) Organic Modifications Urethane Acrylate* Acrylic Acrylic
(t-amine and hydroxy functional)

Inorganic Me/Ph Siloxane, Amino silane Me/Ph Siloxane, Amino silane Amino silane Me/Ph Siloxane (Amine functional) Me/Ph Siloxane Me/Ph Siloxane, Amino silane Me/Ph Siloxane? Amino silane? (Datasheet) Me/Ph Siloxane, Amino silane (Amine)

Hydrogenated Epoxy Acrylic Epoxy Hydrogenated epoxy Hydrogenated epoxy Hydrogenated epoxy

* This material is marketed as a 2nd generation acrylic polysiloxane

Table 2: Level of Organic Modifications Level of Organic Modifications Inorganic:Organic (% wt on binder) 61:39 72:28 77:23 55:45 37:63 58:42 ? 60:40

Product

Urethane Polysiloxane*(A) Acrylic Polysiloxane (B) Acrylic Polysiloxane (C) Epoxy Polysiloxane Acrylic Epoxy Epoxy Polysiloxane Epoxy Polysiloxane Epoxy Polysiloxane (D) (E) (F) (G) (H)

* This material is marketed as a 2nd 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
120

100

Gloss Retention %

80

60

40

20

0 0 2000 4000 6000 8000 10000 12000

Hours Exposure
Urethane Polysiloxane (A) Epoxy Polysiloxane (C) Acrylic Polysiloxane Polyurethane (B)

QUV-A
120

Gloss Retention %

100

80

60

40

20

0 0 500 1000 1500 2000 2500 3000

Hours
Urethane P o lysilo xane (A ) Epo xy P o lysilo xane (D) Epo xy P o lysilo xane (H) A crylic P o lysilo xane (B ) A crylic Epo xy P o lysilo xane (E) P o lyurethane A crylic P o lysilo xane (C) Epo xy P o lysilo xane (F)

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) 82 82 90 82 Epoxy Polysiloxane (F) 77 78 87 76 Polyurethane 10 15 10 15 10 15 10 15

Australia Brisbane Saudi Arabia USA Houston Singapore

* This material is marketed as a 2nd generation acrylic polysiloxane

Figure 2 shows the colour change arising after 12 months external exposure at a coastal UK site and gives an indication of the improvement in colour stability of the Polysiloxane Finishes achieved over an aliphatic acrylic polyurethane. Typically, Polysiloxanes (A and F) show <1 whereas the Polyurethane shows <3. Too early to comment on the external colour change data on the other Polysiloxane Products.

Figure 2 : Colour Retention External Exposure

Colour Retention on External Exposure


3

2.5

DE Colour change

1.5

0.5

0 0 2 4 6 8 10 12 14

Months Urethane Polysiloxane (A) Epoxy Polysiloxane (F) Polyurethane

2.2

Mechanical Properties
The mechanical properties of the Polysiloxane Products are being monitored with time to ensure long-term film integrity. There was a concern that any unreacted alkoxysilyl functionality in the early stages of cure would result in further cross-linking on long-term exposure which in turn may result in stress generation and embrittlement of the films. Results to date reflect the properties of the films up to one month for the majority of the Polysiloxane Products. However results up to two years are available for the Acrylated Urethane (A) and the Hydrogenated Epoxy (F) Polysiloxane products. Flexibility was determined in three ways: 1. 2. 3. Using a Cylindrical Mandrel (ISO 1519). Cupping Test (ISO 1520). By 3 point controlled bending of a 5mm steel panel (zinc rich epoxy primed) to various displacement values (5mm 25mms) and monitoring for signs of cracking of the films with time.

The results show that the acrylated urethane Polysiloxane modification is as expected the most flexible of the Polysiloxane Products evaluated to date even at this early stage. Polyurethane is more flexible than all the Polysiloxane Products evaluated.

This is clearly demonstrated with the 3 point bend results (Figure 3) which shows that the acrylated urethane modification (A) {aka 2nd generation acrylic polysiloxane} is the only one to pass (25mms with no cracking) this test at the highest displacement value after one months external exposure.

Figure 3: 3 Point Bend Flexibility

Epoxy Polysiloxane (F)

Urethane Polysiloxane (A)


(aka 2nd generation acrylic polysiloxane) 6

After two years external exposure the flexibility of the acrylated urethane modified Polysiloxane (sample A) does not change with time suggesting that little, if any, further cross-linking (or degradation of coating) is taking place on ageing. This is in contrast to the Hydrogenated Epoxy modified Polysiloxane which becomes more brittle with time. It is too early at this stage to make comment regarding the longer term properties of the other modified Polysiloxane Products. However, there does appear to be some correlation between hardness, flexibility and internal stress. In general, the harder films with higher internal stress show reduced flexibility when compared to a softer/low stress formulation. The modification with epoxies tends to give fast cure/early hardness but at the expense of long-term flexibility. The acrylics and urethanes on the other hand have slower hardness development but improved long-term flexibility in the long-term. It should be noted that a poorly formulated acrylic could still be hard and inflexible if the ratio of inorganic:organic resin is not carefully balanced. The results do show however that the Acrylated Urethane Modification sample A) gives the best combination of flexibility, low internal stress and hardness albeit the initial hardness is lower (with one exception - E) than the other modifications. Consequently, and together with the weatherability results, it might be expected that the Acrylated Urethane Polysiloxane Modification (A) will give the best long-term performance on long-term environmental exposure.

2.3

Formulation Development
In addition to the type and level of Organic modification used to achieve the desired film properties, formulation development is important to achieve for example storage stability of coatings and adhesion of the Polysiloxane Coatings to Organic Base Coats. It should be noted that the adhesion of Polysiloxane Coatings to Organic Base Coats is not universal i.e. is more variable and not as consistent as with Polyurethane Coatings. At the present time this is best determined by experiment. The organic modification is important in the tolerances of Polysiloxane Coatings to organic primers or high builds. Epoxy modified Polysiloxanes do tend to show a wider overcoating window over Organic Base Coats. A key property of Polysiloxane Coatings is the in-can storage stability, especially at elevated temperatures of 30C 40C. The functionality of the siloxanes/silanes employed in typical polysiloxane formulations are usually moisture sensitive and trace amounts of water can result in a rapid increase in viscosity due to oligimerisation of the alkoxy groups present. This reaction can have a negative effect on both the dry times and long-term physical properties such as flexibility and durability. The normal test for storage stability is to measure the viscosity after storage at 40C over a period of six months. The Polysiloxane formulations are very sensitive to the raw materials and each one must be carefully screened before use. One of the most critical is titanium dioxide as the surface treatment and pH can catalyse condensation reactions in the siloxane resins resulting in increasing viscosity. The curing agents employed are very often amino silanes or amino silane/amine blends which are very moisture sensitive. Long-term storage stability of the curing agent can be affected by catalyst and moisture levels. Two of the Polysiloxane Products tested show unacceptable storage stability.

3.

CONCLUSION
Polysiloxane Technology offers a low VOC, non-isocyanate, high performance Finish alternative to Polyurethane Technology. Development of this Technology will continue apace and much needs to be done to develop a knowledge base to further exploit this Inorganic Organic Hybrid Technology.

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