POLYSILOXANE TOPCOATS PRODUCT CHOICE FOR OPTIMUM PERFORMANCE Adrian F.

Andrews International Protective Coatings Akzo Nobel England

Abstract: Organic coatings degrade as a result of thermal oxidation, photo-initiated oxidation or by chemical attack. Silicon based inorganic coatings are much more resistant to these degradation mechanisms and Polysiloxane coatings offer significantly enhanced durability when compared to Polyurethane coatings. Polysiloxane coatings must however be modified to the right extent with organic resins to enable other coating performance properties such as flexibility, toughness, adhesion to primers and cost to be obtained while at the same time not detracting from the Polysiloxane properties. This paper discusses Polysiloxane Topcoats together with the level and type of organic modification necessary to optimise coating systems performance in corrosive environments.

Non-isocyanate Finish Technologies developed to date have too high a VOC content, have reduced weathering characteristics, poor low temperature cure and reduced mechanical properties when compared to the versatile polyurethane coatings. The high VOC, very thin film fluoropolymer based finishes, whilst offering the potential of superior weatherability, have met with mixed results in the field and in some cases offering no better durability than aliphatic acrylic polyurethanes. Organic coatings including polyurethanes will degrade (thermal oxidation, photo-initiated oxidation and chemical attack) resulting in deterioration of film properties leading to gloss loss, discolouration, embrittlement and adhesion loss. In contrast Inorganic Coatings based on silicon are much more resistant to the above degradation mechanisms. The two main reasons for this are:

INTRODUCTION 1. Conventional High Performance Coatings Systems currently being offered to afford long term (10 - 15 years) corrosion protection are largely organicbased and are typically derived from zinc based primers (inorganic zinc silicate or zinc rich epoxies), high build epoxies and Polyurethane Finishes. Health, Safety and Environmental (HSE) legislation is ever increasing and Polyurethane Finishes generally available have a VOC of 340gl-1 and more typically 420gl-1 although recently 250gl-1 Polyurethane Finishes are being trialled in California due to the impending very strict VOC legislation. The other concern with polyurethanes is the pulmonary sensitisation potential of low mw volatile isocyanates when being airless sprayed. 2. the higher bond strengths of the Si O bond (452 kJmol-1) which form the backbone of the inorganic polymer chain make them more heat and UV resistant compared to the C C bond strength (350 kJmol-1) of the organic polymer chain; and the Si O bonds are already oxidised making them resistant to atmospheric oxygen and most oxidising chemicals.

For these reasons many attempts to utilise silicate technology (hydrolysed tetra ethyl ortho silicate or alkali metal silicate) have been made to develop high gloss finishes but have been unsuccessful due to the need to pigment at high PVC to prevent film cracking resulting in matt finishes.

The use of silicone based materials have generally been limited by the need to heat to achieve cross-linking and in many instances the ability to achieve films of sufficient toughness and adhesion for general use. Hydrolytic polycondensation reactions of alkoxy silyl functional polyorganosiloxanes (Figure 1) offers the potential for ambient curing. Little progress was made in exploiting this technology until the publication of a patent in the early 1980s claiming Interpenetrating Networks (IPNs) comprising an epoxy amine network and a polysiloxane network. Significantly more progress has been made in the last 5 - 7 years with the publication of a number of patents covering a range of methods of modifying the inorganic network by organic polymers together with the commercialisation of a number of products. Inorganic-Organic Hybrid Coatings based on polysiloxane resins with varying organic modifications have been developed which provide non-isocyanate ambient curing viable films offering good HSE characteristics (low VOC, low toxicity) good appearance and superior weatherability when compared to aliphatic acrylic polyurethanes. Extensive corrosion testing has demonstrated that typical high build epoxy/polyurethane intermediate systems over zinc primers can have the 200 - 250 microns of organic coating replaced by 125 microns of the organically modified polysiloxane. The use of two coat systems rather than three does however require greater care during application by applicators to ensure the correct dry film thickness is achieved. The organically modified Polysiloxane Finish thus allows reduced application costs (two coats instead of three) and from performance projections, reduced life cycle costs due to the increased weatherability and durability when compared to conventional aliphatic acrylic Polyurethane Finish coating systems.

CURRENT POSITION Organic Modification Organic modification is necessary to achieve a balance of film properties, such as adhesion, flexibility, and cost. Using various organic modifications it has been found that around 20% - 30% organic modification gives the optimum performance in terms of both adhesion and durability on exterior exposure and accelerated testing. Too low a level of organic modification results in films which have too high a polysiloxane characteristic i.e. glass-like and results in films cracking and losing adhesion on prolonged testing. This was shown to be the case when the level of organic modification of the polysiloxane was 8% (Figure 2) and applied to a range of primers (zinc silicate, zinc phosphate, zinc epoxy) and subjected to prolonged (>6000 hrs) accelerated testing (e.g. Salt Spray - ISO 7253, Prohesion - ASTM G85, Norsok Cycle - Modified NACE TM0184, Cyclic Test ASTM D5894, Condensation - ISO 6270, QUV - ASTM G53). Interestingly this was only observed when the films were subjected to a full drying out period during the accelerated test (which does not form part of any of the Accelerated Tests above). Consequently the use of non-standard test methods e.g. water immersion 1000 hrs - ISO 2812 followed by 1 week drying out was developed to more quickly identify the mode of failure and to ensure there were no weaknesses in the coating systems. Also of interest is that these same films when exposed externally for a period of 5 years in a C4 environment have shown only minor defects around the scribe. Too high a level of organic modification detracts from the polysiloxane properties and compatibility may become a problem. The type of organic modification employed should detract as little as possible from the polysiloxane properties. For example, to avoid poor colour stability, aromatic epoxies would not be employed as the organic modification. The first Polysiloxane Finish to be commercialised was organically modified with a hydrogenated epoxy. Subsequently second generation polysiloxane products with acrylated urethane and acrylic have been developed.

The use of acrylated urethane and acrylic modifications should in theory detract less from the properties of the polysiloxane resin and is more likely to give improved durability and colour retention whilst not detracting from overall corrosion resistance when compared to hydrogenated (or aliphatic) epoxies. Much work has concentrated on the area of comparison of acrylated urethane modification (A) compared to the commercially available epoxy modified product (B). The acrylic (C) is a more speculative approach and utilises a different process to that of the commercially available acrylic (D) which is a simple blend of an acrylic and polysiloxane resin. Consequently less data is available on the acrylic modified polysiloxanes than on the epoxy and acrylated urethane modified polysiloxanes. CHEMISTRY The networks produced are complex due to multi cross-linking reactions. Both the acrylated urethane and epoxy modified polysiloxanes are cured with an amino alkoxysilyl functional silane. In addition to these organic reactions, (amine-epoxy and pseudo Michael addition of amine-acrylated urethane) hydrolytic polycondensation reactions (catalysed by water) occur between the alkoxysilyl groups of the curing agent and the polysiloxane resin (Figure 3). The potential for other reactions to take place exist. The complexity is further enhanced when the effects of temperature and relative humidity on both the organic and inorganic reactions taking place are considered. GENERAL PROPERTIES The general properties of the Polysiloxane Finishes are shown in Table 1. The volume solids of these materials must be measured due to the significant levels of alcohols generated during the condensation reaction of the polysiloxane resin and aminosilane curing agent. The epoxy modified polysiloxane can be formulated with no added solvent whereas the acrylated urethane and acrylic modified polysiloxanes do employ the addition of a little solvent (VOC still less than 250gl-1) which gives better general application properties. It should be noted that the adhesion of Polysiloxane Finishes to organic primers and high builds is not universal i.e. is more variable and not as consistent as with Polyurethane Finishes. At the present time this is best determined by experiment.

DURABILITY Figure 4 gives an indication from accelerated weathering using QUV-A of the improvement in durability achieved over aliphatic acrylic polyurethanes. An approximate view of effectiveness is to consider the time taken for the finish to lose 50% of its initial gloss. If this accelerated testing could be translated into real life then the epoxy modified polysiloxane would give 3 - 4 times the durability of polyurethane and the acrylated urethane modified polysiloxane 4 - 5 times. Table 2 shows exterior exposure data after 4 years in C4 and C5 (ISO 12944 classification) environments for the acrylated urethane and epoxy modified polysiloxanes. This data supports the ranking shown in QUV-A data although the result in Singapore for the epoxy modified polysiloxane is lower than expected! Figure 5 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 aliphatic acrylic polyurethane. CORROSION RESISTANCE Tables 3, 4 and 5 show the accelerated test results for the Polysiloxane Finishes applied as a single coat (125 microns) over zinc rich epoxy, zinc silicate and zinc phosphate epoxy primers (75 microns) respectively. Generally, the only breakdown is underfilm creep from the scribe with no face breakdown in terms of cracking, flaking or blistering. In all the tables, the data refers to underfilm corrosion in mms from the scribe. No creep is 0mm and an excellent result, 3 - 4mms are generally considered good with up to 6mms being acceptable and above 6mms the result is considered to be poor. It is immediately apparent that over the range of anti-corrosive tests the two coat 200 micron dft polysiloxane systems give similar if not better performance than the three coat 325 micron dft conventional high performance system. This performance has been verified by an external independent testing laboratory for the two coat polysiloxane (acrylated urethane-A and acrylic-C modifications) systems over zinc rich epoxy primer. Similar conclusions can be drawn from Tables 4 and 5.

Table 6 shows the exterior exposure results after periods of up to 4 years in coastal marine environments (C5 - ISO 12944). These clearly show that zinc primers give significantly better performance than non-zinc primers in terms of underfilm creep from the scribe. The magnitude of the difference between the zinc primed systems and the non-zinc primed systems is significantly greater than that shown by any of the accelerated tests. Comparison with conventional three coat zinc primed and non-zinc primed (barrier and zinc phosphate) systems shows these to give similar results i.e. negligible scribe creep with zinc rich primer and typically 5 10mms with non-zinc primers. This suggests that for offshore, coastal and marine corrosive environments zinc rich primer should always be used and other primers limited to less aggressive environments. MECHANICAL PROPERTIES The mechanical properties of the organically modified polysiloxanes were monitored with time (up to 12 months) to ensure long term film integrity. There was a concern that any unreacted alkoxy silyl groups 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. The properties monitored were amongst others fracture toughness (Figure 6), tensile strength (Figure 7), elongation at break, (Figure 8) and flexibility. Flexibility was determined in two ways: 1) 2) using a cylindrical mandrel (Table 7) and; by controlled blending of a 5mm steel panel (zinc rich epoxy primed) to three displacement values (15mms, 20mms and 25mms) and monitor for signs of cracking (Table 8 and Figures 9 and 10).

The acrylated urethane modified polysiloxane (A) develops its coatings properties over 1 month compared to 1 week for the epoxy (B) and acrylic (C) modified polysiloxanes. This may be explained in terms of the reaction kinetics of the organic reactions taking place to form a network. The rate constants k1 and k2 for the epoxy-amine and acrylated urethane-amine reactions are outlined below. AmineAcrylated Urethane 2.88 x 10-4 7.06 x 10-6

Chemistry k1 (1mol-1g-1) k2 (1mol-1g-1)

Amine-Epoxy 5.05 x 10-5 2.98 x 10-5

From the reaction kinetics it can be determined that the epoxy-amine reaction achieves 80% conversion in 24 hours at 20C whereas the acrylated urethaneamine reaction takes 100 hours at 20C to achieve the same extent of reaction. Once the coatings properties have been developed there is little change over a 12 month period suggesting that little if any further cross-linking is taking place with any unreacted alkoxysilyl functionality. FUTURE POSITION The superior performance and beneficial HSE characteristics exhibited by organically modified polysiloxanes ensures their continued development. It should be recognised that Inorganic Organic Hybrid Technology is a new technology and there is no real knowledge database to fall back on as is the case with organic (epoxy, polyurethane) technologies. It is critical to understand the network characteristics and structure-property relationships and the extent to which these can be carried through coatings design if new coatings with well defined, reproducible performance characteristics are to be developed. In the absence of this information new coatings development utilising this technology will be reliant on testing a wide range of formulations potentially increasing both the product development time and the uncertainty regarding long term coating performance.

From these results it can be seen that the acrylated urethane modified polysiloxane (A) is tougher and more robust than the epoxy modified polysiloxane (B) or the acrylic modified polysiloxane (C) and would be expected to give the best long term performance in terms of film integrity. This is clearly demonstrated in Figure 9 where cracking occurs across the panel with the epoxy modified polysiloxane (B) whereas the acrylated urethane modified polysiloxane (A) shows no cracking even at a greater displacement value.

SUMMARY For optimum performance it is important to choose the right organically modified polysiloxane. The acrylated urethane modified polysiloxane shows improved long term performance benefits in terms of durability (gloss and colour retention), flexibility, film toughness and edge protection when compared to the epoxy modified polysiloxane. On the other hand the epoxy modified polysiloxane shows improved early hardness as a result of faster development of film properties. All of the organically modified polysiloxanes discussed from a series of accelerated tests and exterior exposure would be expected, when part of a two coat zinc rich primed system, to have significantly better long term performance than a conventional three coat system.

APPENDIX

FIGURE 1

Si OR + H2O Si OH + RO Si Si OH + HO Si

Si OH + ROH Si O Si Si O Si + ROH + H2O

Figure 1.

Hydrolytic Polycondensation Reactions of Alkoxysilyl Functional Polysiloxanes

FIGURE 2

Figure 2.

Cracking and adhesion loss of Polysiloxane Films modified with 8% Organic when applied over a range of Primers

FIGURE 3

1.

R'NHR'' +

O Epoxy R'R''N

OH

R'NHR'' +

COO Acrylated Urethane

R'NR''

COO

2.

(RO)3-n(R'')nSi

OSi(R'')2

OSiR''(OR)

OSi(OR)3-n(R)n

Hydrolytic Polycondensation (Ref Fig. 1.)

Si

Si

3.

Hydrolytic Silanol condensation reactions between 1. and 2.

R' R'' R n a, b, m

= = = = =

e.g. (RO)3-nR''nSi(CH2)m e.g. Alkyl, Aryl, Hydrogen Alkyl 1, 2 Integers

Figure 3.

Multi Cross-linking Reactions producing Complex Networks

TABLE 1

Property

A (Acrylic Urethane) Measured 78

B (Epoxy)

C (Acrylic)

D (Acrylic)

Volume Solids (%) ISO 3233

Measured 90

Measured 82

Measured 76 Datasheet 90 170

VOC (g/litre) EPA Method 24 Hard Dry (hrs) ISO 9117 50% RH 10C 20C 40C Initial Gloss (%) ASTM D523 Heat Resistance 1 month at 130C Adhesion (P.A.T.) ISO 4624 over Zinc Rich Epoxy Primer

172

120

150

12 8 4 70 - 80 Very slight yellowing

11 6 3 80 - 90

12 6 4 80 - 90 Very slight yellowing

10 6 70 - 80 Very slight yellowing

Yellowing

13 MPa

13Mpa

11 MPa

Table 1.

General Properties of Polysiloxane Finishes

FIGURE 4

Polysiloxane Quv A
120

100

Gloss Retention %

80

60

C A D B PU B PU C

A, D
40

A (Acrylic) Polyurethane B (Epoxy) C (Acrylic) D (Acrylic)

20

0 0 2000 4000 6000 8000 10000 12000

Hours

Figure 4.

QUV-A, Polysiloxane Finishes

TABLE 2

Gloss Retention (60) Blyth, UK Houston, USA Brisbane, Australia Singapore C5M/I C4 C4 C5M/I

A 90 95 90 95 85 90 85 90

B 80 85 85 90 80 85 55 60

Table 2.

Exterior Exposure of Polysiloxane Finishes

FIGURE 5

External Exposure of Polysiloxanes

3

2.5

A (Acrylated Urethane) Polysiloxane B (Epoxy) Polysiloxane Polyurethane

Delta E
1.5

A, D PU B

0.5

0 0 2 4 6 8 10 12 14

Months

Figure 5.

Colour Change of Polysiloxane Finishes on External Exposure

TABLE 3

SYSTEM A (Acrylated Urethane) - 125m 0.2 B (Epoxy) - 125m 1.5

ZINC RICH EPOXY (75m) C (Acrylic) - 125m 1.0 (4000 hrs) 0 (4000 hrs) D (Acrylic) - 125m 1.0 (4000 hrs) 0 (4000 hrs) 1.8

6000 hrs Acc. Testing Corrosion Creep (mms)

HP Epoxy PU

(200 m) (50m)

ISO 7253 Salt Spray ASTM G85 Prohesion BS 3900 Cold Salt Spray ISO 2812 40C Immersion Norsok Cyclic M501 (4200 hrs) ASTM D5894 Cyclic (4032 hrs) *

0.5

0.5

3.3

1.5

0*

2.5

0.5

4.6

0.9

1.6

2.2

No blistering at 4000 hrs but thereafter small blisters develop. Blisters do not occur if the film is fully dried out every 1000 hrs.

Table 3.

Corrosion Resistance of Polysiloxane Finishes over Zinc Rich Epoxy Primer

TABLE 4

SYSTEM

INORGANIC ZINC SILICATE PRIMER (50 - 75m) A (Acrylated Urethane) - 125m 0.9 B (Epoxy) - 125m 0.2 1.8

6000 hrs Acc. Testing Corrosion Creep (mms)

HP Epoxy PU

(200 m) (50m)

ISO 7253 Salt Spray ASTM G85 Prohesion BS 3900 Cold Salt Spray ISO 2812 40C Immersion Norsok Cyclic M501 (4200 hrs) ASTM D5894 Cyclic (4032 hrs) *

0.7

3.3

1.5

0*

1.0

1.3

4.6

1.9

2.1

2.2

No blistering at 4000 hrs but thereafter small blisters develop. Blisters do not occur if the film is fully dried out every 1000 hrs.

Table 4.

Corrosion Resistance of Polysiloxane Finishes over Zinc Silicate Primer

TABLE 5

SYSTEM

HIGH SOLIDS ZINC PHOSPHATE PRIMER (75m) A (Acrylated Urethane) - 125m 5.0 B (Epoxy) - 125m 2.8 3.2

6000 hrs Acc. Testing Corrosion Creep (mms)

HP Epoxy PU

(200 m) (50m)

ISO 7253 Salt Spray ASTM G85 Prohesion BS 3900 Cold Salt Spray ISO 2812 40C Immersion Norsok Cyclic M501 (4200 hrs) ASTM D5894 Cyclic (4032 hrs)

2.8

2.8

3.5

0.5

0.4

2.5

3.1

2.7

5.5

7.9

8.0

4.1

Table 5.

Corrosion Resistance of Polysiloxane Finishes over Zinc Phosphate Epoxy Primer

TABLE 6

Urethane Polysiloxane (A) (mm creep) PRIMER 4 years Blyth Zinc Silicate (75m) Zinc Rich Epoxy (75m) HS Zinc Rich Epoxy (75m) Zinc Phosphate Epoxy (75m) HS Surface Tolerant Epoxy (150m) HS Epoxy Mastic Aluminium (150 m) HS Glass Flake Epoxy (200m) 0 2 years Bohus Malmon 0

Epoxy Polysiloxane (B) (mm creep) 4 years Blyth 2 2 years Bohus Malmon 1

0.5

13

12

10

15

13

18

12

12.5

10

12

10

Table 6.

Exterior Exposure Corrosion Resistance of Polysiloxane Finishes

FIGURE 6

1.5 1.2
-3/2

) Kic (MNm 0.9 0.6 0.3 0 0 1 2 3 4 5 6 7 8 9 10 11 12 Time (Months)

A (Acrylated Urethane Modification) B (Epoxy Modification) C (Acrylic Modification)

Fracture Toughness (MNm-3/2) Coating A (Acrylated Urethane Modification) B (Epoxy Modification) C (Acrylic Modification) Before Exposure 0.61 1 Month ( std error) 1.36 ( 0.07) 0.75 ( 0.02) 0.69 ( 0.04) 3 Months ( std error) 1.43 ( 0.08) 0.77 ( 0.04) 0.78 ( 0.05) 6 Months ( std error) 1.43 ( 0.08) 12 Months ( std error) 1.48 ( 0.09) 0.80 ( 0.03) 0.73 ( 0.02)

0.87

1.14 ( 0.16)

0.59

0.80 ( 0.04)

Figure 6.

Fracture Toughness of Polysiloxane Finishes

FIGURE 7

30 25 Tensile Strength (MPa) 20 15 10 5 0 0 1 2 3 4 5 6 7 8 9 10 11 12 Time (Months)

A (Acrylated Urethane Modifciation) B (Epoxy Modification) C (Acrylic Modification)

Tensile Tests Coating A (Acrylated Urethane Modification) B (Epoxy Modification) C (Acrylic Modification) Before Exposure UTS eb M 13.0 10.2 0.45 1 Month UTS eb M 22.9 5.2 1.1 6 Months UTS eb M 26.8 3.3 1.32 12 Months UTS eb M 24.5 3.8 1.2

22.2

2.8

1.1

24.3

2.8

1.3

25.3

2.1

1.4

18.5

1.5

1.4

9.3

4.4 UTS eb M

0.39 = = =

10.9

2.0

0.73

13.0

1.2

0.97

10.9

1.2

1.1

Ultimate Tensile Strength Elongation at break Modulus

Figure 7.

Tensile Strength of Polysiloxane Finishes

FIGURE 8

12

10 Elongation at Break (%)

A (Acrylated Urethane Modification) B (Epoxy Modification) C (Acrylic Modification)

0 0 1 2 3 4 5 6 Time (Months) 7 8 9 10 11 12

Tensile Tests Coating A (Acrylated Urethane Modification) B (Epoxy Modification) C (Acrylic Modification) Before Exposure UTS eb M 13.0 10.2 0.45 1 Month UTS eb M 22.9 5.2 1.1 6 Months UTS eb M 26.8 3.3 1.32 12 Months UTS eb M 24.5 3.8 1.2

22.2

2.8

1.1

24.3

2.8

1.3

25.3

2.1

1.4

18.5

1.5

1.4

9.3

4.4 UTS eb M

0.39 = = =

10.9

2.0

0.73

13.0

1.2

0.97

10.9

1.2

1.1

Ultimate Tensile Strength Elongation at break Modulus

Figure 8.

Elongation at Break of Polysiloxane Finishes

TABLE 7

Polysiloxane (Organic Mod) A (Acrylated Urethane) B (Epoxy) C (Acrylic)

Minimum Diameter (inches) that Coating Passed 1 Week 3/16 1 Month 1/4 3 Months 3/8 6 Months 3/8 12 Months 3/8

3/8

>1

>1

>1

3/16

>1

>1

>1

Table 7.

Cylindrical Mandrel Flexibility of Polysiloxane Finishes

TABLE 8

MAXIUMUM DISPLACEMENT WITHOUT FAILURE Exterior Exposure 1 Week A (Acrylated Urethane) B (Epoxy) C (Acrylic) 15mm 1 Month 25mm 3 Months 25mm 6 Months 25mm 12 Months 25mm

20mm

15mm

<15mm

<15mm

<15mm

15mm

15mm

15mm

15mm

15mm

Table 8.

Panel Bend Flexibility of Polysiloxane Finishes

FIGURE 9

A (Acrylated Urethane)

B (Epoxy)

Figure 9.

Panel Bend Flexibility of Polysiloxane Finishes

FIGURE 10

Figure 10.

Equipment used to Bend Panels