For more than fifty years solvent-based silicone resins have been used for the coating of objects, which are exposed to high temperatures (>200 °C), such as boilers, engines, exhaust stacks, heat exchangers, mufflers, barbecue equipment, etc.
Due to environmental concerns and regulations, recent efforts by silicone resin manufacturers and powder coating formulators have expanded the utility of silicone-based technologies into the field of powder coatings [305, 306]. Silicone resins are structurally based on a framework of Si-O and Si-C bonds. They provide excellent heat and weathering resistance, but also inertness to chemicals and good electrical characteristics. These properties are due to the stability of the Si-O-Si bond, stability of organic radicals attached to the Si atom, (because of the screening effect of the siloxane bond), the formation of stable Si-O-Si bonds within the polymer upon partial disintegration (in contrast to organic radicals) thus preventing film disruption, and the insulating effect of the siloxane layer (formed during thermal oxidation).
Excellent heat-resistant properties will be provided by pure silicone polymers, but for most practical applications, the organic-modified silicones meet the requirements for the majority of specifications. Most silicone resins are produced by the co-hydrolysis of di- and trichlorosilanes. The resulting di- and trisilanol moieties are highly reactive and the majority will immediately condense to form a polymeric resin matrix. Therefore hydrolysis and polycondensation are generally performed in one step. Polycondensation between silanediols yield straight-chain polymers;
Whereas similar reactions between silanetriols result in the formation of highly crosslinked polymer molecules:
- The strenght of the Si-O bond significantly exceeds that of the Si-Si or the Si-C bonds. That means there is a strong tendency for the two elements (Si and O) to combine and to build up polymers, in which the structural unit.
- Reactions of carbon conpounds tend to produce only five-or six-membered rings, whereas silicone rings of relatively large size may be formed quite readily. It seems, therefore, according to Groggines that cyclization competes more seriously with chain-polymer formation in the reactions of the silicone atom, than it does in carbon chemistry.
Synthesis of the before mentioned chlorosilanes can be carried out by means of the wellknown Grignard reaction, by reacting silicon tetrachloride with alkyl magnesium bromide: Another, more direct way of preparing chlorosilanes, involving the reaction of silicon with alkyl- or arylchlorides, with the use of copper or silver catalysts is also possible [307]. Both
methods produce a mixture of the various chlorosilanes, which leads, after hydrolysis, also to a mixture of the various silanols.
Silanol groups, which remain unreacted during the following polycondensation, can be condensed after application of the coating or co-reacted with organic polymers. Due to the electro-negativity of the Si atom, a hydroxy group attached to a silicon atom is more polar and therefore more acidic than its carbon analog (carbinol).
As a result, reactions between silanol functional resins and hydroxyl functional organic polymers will take place at relatively low temperatures (110 to 115 °C).
The cure scheme for a silicone-based powder coating is dependent on the silicone content and the selection of the organic co-binder.
A typical cure for a coating, based on 100 % silicone would be 30 min at 230 to 250 °C. Cerium acetylacetonate can accelerate the stoving process [306]. Silicone resins are high molecular weight polysiloxanes, which mostly contain
methyl- and/or phenyl groups as organic substituents. Methyl silicone resins are harder and less thermoplastic than phenyl silicones, but less heat resistant, because of the greater sensitivity to oxidation of the CH3 groups. Pure methyl silicones have, due to the relative small mass of the methyl group, a lower C-content and a higher SiO2-content than the phenyl types. A disadvantage is that they are not compatible with other organic resins. Phenyl silicone resins have good heat stability up to temperatures of 250 °C, but like all organic groups, they will decompose at about 400 °C.
While they are claimed to be the betterchoice for heat resistance in the intermediate range (100 to 375 °C), it should be remarked, that when the organic component is oxidized, the losses in film weight of phenyl groups will be higher than those of methyl groups. Additionally, the reactive silanols, sharing a silicon atom with a phenyl group are sterically hindered. This can result in poor cure and reduced physical properties. The main advantage of phenyl silicones is their compatibility with other organic resins. Compatibility is essential to ensure miscibility with the resin components, reducing the tendency to cross-contamination problems and film disruption, and at the same time improving physical properties.
An important factor affecting the suitability of a silicone resin is the crosslink density or degree of substitution. In the natural state the four valency sites of a silicon atom are bound with oxygen. Silicone-based resins are created by substituting one, two, three or four of these oxygen atoms with a variety of moieties. The number of substituted oxygens per silicon atom is called the “degree of substitution”. In the case of conventional silicone-based coating resins, phenyl and methyl groups are most often utilized, and commercially available silicone resins possess degrees of substitution within a range from 1.0 to 1.8. In this range the physical form of the resin can vary from a hard brittle solid to a viscous liquid.
Physical properties are also affected by the molecular weight and residual silanol (SiOH) content of the resin. If highest heat resistance is required, a powder coating will be formulated with a 100 % silicone. This will provide the best thermal properties in applications, where heat resistance has a higher priority than organic compatibility. A resin with a balanced phenyl/methyl
ratio and highest allowable degree of substitution should be selected.
For less stringent applications a silicone resin with high phenyl content should be used allow for mixing with organic resins, to reduce raw material costs and to improve the physical properties of the coating. Selection of the right pigments to achieve maximum temperature resistance is very important. Coatings with short-term exposures (<1000 hours) at up to 350 °C, or long-term exposures up to 225 °C can be produced with TiO2 and mica. Applications with short-term up to 525 °C or long-term exposures up to 250 °C often include heat resistant black iron oxides.
Aluminum, zinc and stainless steel powders are used for high temperature applications, in the short term up to 650 °C or long term at 350 °C. The inclusion of metal pigments with their high thermal conductivity prolongs the life of the
coating by conducting heat away from the coated substrate. Additionally, the inclusion of metal pigments compensates for the
inevitable oxidation of the silicone resin at high temperatures by stabilizing the coating as the metal fuses with the resin to form a ceramic coating with stable metalsiloxane bonds. Similarly, ceramic frits are used to create durable coatings, which are stable up to 750 °C [305].
DuPont [308] claimed that the addition of up to 50 % of alkali tetraborate will lead to a heat stability of at least 550 °C, suitable in particular for boilers, ovens, heat exchangers, and cooking utensils. Enhancements to the thermal stability of the coating can also be achieved by increasing the amount of lamellar fillers (such as mica), or incorporation of anti-oxidants.
Table below [306, 309] gives typical formulations for a matt black and a glossy white silicone-based powder coating. In the mid-nineties, also silicone elastomeric powders have been introduced [305, 310].
A. Silicone powder coating with good color stability and heat resistance up to 300 °C
| Material | Parts by weight |
|---|---|
| Silres 604″ (1)” | 56.3 |
| Crylcoat 2617-3″ (2)” | 11.0 |
| “ß-hydroxyalkyl amide” (3) | 0.7 |
| Blanc Fixe F” (4)” | 10.0 |
| Synergy Red 6054″ (5)” | 20.0 |
| Resiflow PV88″ (6)” | 1.5 |
| Benzoin | 0.5 |
| Properties | Value |
|---|---|
| Curing conditions | 30min/230 to 250 °C |
| Properties: Film thickness | 40 to 60 μm |
| Pencil hardness | 4 H |
| Gloss 60° | 74 % |
| Gloss 60° after 20 h 265 °C | 29 % |
| Crosshatch | GT 1 |
| MEK-resistance | >200 DR |
B. Silicone powder coating with corrosion and high heat resistance
| Material | Parts by weight |
|---|---|
| Silres 604″ (1)” | 47.5 |
| FERRO PK 3095″ (7)” | 15.0 |
| “Glimmer TM” (8) | 11.0 |
| Heucophos SAPP” (9)” | 13.5 |
| Talkum EL–10″ (10)” | 12.3 |
| Resiflow PV88″ (6)” | 0.3 |
| Benzoin | 0.4 |
| Properties | Value |
|---|---|
| Curing conditions | 30min/230 to 250 °C |
| Properties: Film thickness | 40 to 60 μm |
| Pencil hardness | 4 H |
| Gloss 60° | 15.4 % |
| Gloss 60° after 1 h 500 °C | 12.8 % |
| Crosshatch | GT 1 |
| Impact resistance (dir.) | > 80 inch·lbs |
(1) Methyl polysiloxane (Wacker Chemie AG)
(2) Polyester (Cytec)
(3) “VESTAGON HA 320”(Evonik Industries) or “Primid XL-552” (Ems)
(4) various suppliers
(5) Pigment (Engelhard)
(6) flow agent, (Worlée)
(7) iron oxide (Ferro)
(8) mica filler (ASpanger Mineralwerke)
(9) anticorrosion pigment (Heubach GmbH)
(10) Talcum (Luzenac-Europe)
These soft and flexible spherical particles (average
particle size 3 to 5 µm) can be incorporated into powder coating formulations to create coatings with unique appearance, texture and feel. With doses of 5 to 15 % they give tough textured finishes. At higher levels suede or soft-feel coatings can be produced. DuPont [311] claims the use of low-melting glass particles to fill voids in the film and prevent adhesion failure.
Dow Corning have commissioned a study by the University of Southern Mississippi.The results of the study are described by researchers from Dow Corning, Dow Chemical and the University of South Mississippi [312]. The study concentrated on three themes: the effect of pigment volume concentration (pvc); the effect of silicone resin composition, using four Dow Corning silicone resins; and the compatibility and high temperature performance of silicone-polyester at ratios of 70:30 and 30:70.
For all their experiments they used a high temperature resistant spinel black pigment. The conclusions of their studies can be summarized as follows:
- The most suitable PVC level is 24%.
- Film thickness should be kept below 40 µm, to avoid solvent popping and wrinkling;
- All tested solid silicone resins can be used to formulate high temperature resistant powder coating (a heat exposure test of 1000 hours at 45 C can be realized using the spinel black pigment);
- It is important to match silicone/organic powder coating blends using polymers of similar viscosities and reactives.
The problem of solvent popping is thought to be caused by water, evolved due to silanolsilanol condensation.
Acrylic-silicone powder coating resins are described by a team of researchers at the Glidden Co. [313]. They blended a hydroxyl acrylic resin with a solid silicone resin and cured the blend with a blocked isophorone diisocyanate adduct. The preferred silicone resin is a hydroxy functional low molecular weight cyclic silicone intermediate (“DC-Z-6018”), having a number average molecular weight of about 600. The hydroxyl functional acrylic polymer and the silicone resin are dry blended in a weight ratio of between 50 and 75 % acrylic resin and between 25 and 50 % cyclic silicone. It is shown by accelerated weathering, that gloss retention is much higher for the silicone containing materials (particularly at the 50 % level) than for the acrylic resin without any silicone resin.
The same researchers [313] attempted to make a graft copolymer of silicone-acrylic, but this failed, due to the high reactivity of the silanol hydroxyl (SiOH) groups. But, upon reacting the silanol hydroxyl groups with fluorinated alcohols before grafting the acrylic monomers, a graft copolymer of silicone-acrylic can be successfully made. It is believed, that the weathering resistance of this fluorinated silicone-acrylic copolymer should be excellent.
In a patent [314] of Rohm and Haas the use of trifluoromethane sulfonic acid diethylamine salt as a wrinkling agent in silicone based powder coatings is claimed.
A paper by Rawlins and Thames [315] reports the synthesis, characterization and evaluation of novel silicone modified polymers as clear UV curable powder coatings. These polymers are described as acrylated, silylated diglycidyl ethers of bisphenol A (DGEBA).They are synthesized by reacting acrylic acid with DGEBA polymers in the presence of a base catalyst and free radical inhibitors. Silylation is realized by the addition of 10 mol-% excess of hexamethyl disilazane to the washed acrylated DGEBA. UV curable powders are made by adding two photoinitiators to each of the silicone modified polymers, and melt mixing and grinding them in the usual way.Though the silylated modifications of DGEBA polymers are likely to be of academic interest only [316], there are some interesting facts arising from this study. The most important ones concern the low melt viscosities, achieved with these polymers (without sacrificing storage stability) and the complete freedom from surface defects, such as cratering and orange peel, obtained without the addition of flow control agents.
Wacker [317] reported the use of solid silicone-polyesters in conventional thermoset powder coatings, leading to a higher heat- and UV resistance compared to the pure polyesters. Silicone modification reduces the polymer-Tg by nearly 32 % from the starting polymer.
The use of silicone resins for high-temperature resistant powder coatings is still in its infancy and a lot of new developments and applications are to be expected from this interesting field of special powder coatings in near future.
Reference:
Powder coating chemistry and technology
Author:
Pieter Gillis de lange
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