Securoc & Portaflame. An expedient flame protection system for plastics. The perfect match.

Securoc & Portaflame in PVC

Ankerpoorts flame retardants tackle smoke and HCl emission
The Products Mineral flame-retardants based on Aluminium Hydroxide (Portaflame SG), Magnesium Hydroxide (Securoc B), and special Huntite/Hydromagnesite blends (Securoc C) have shown to be efficient flame retardants and smoke suppressants in PVC applications. The products are derived from either natural or synthetic raw materials by grinding, air classification, coating and other operations by Ankerpoort at its plants in Netherlands, Belgium and Greece . Due to careful choice of raw materials and distinct processing know how tailor made products and high consistency are achieved. Ankerpoort plants are holding ISO-9001 certificates. More specific product data are available in data sheets and our technical brochures. Fire Performance of PVC Generally, because of its chlorine content PVC is less flammable than most of the polymers. So Rigid PVC is usually self-extinguishing, but with increasing levels of organic additives such as plasticizers, lubricants, modifiers etc. fire performance becomes significantly inferior. Traditionally, enhanced fire performance of PVC Compounds is achieved by addition of 2 to 6 parts of antimony trioxide (Sb2O3) that acts as efficient synergist in the fire-retarding role of chlorine. Alternatively (or additionally) phosphate plasticizers, chloroparaffines or brominated compounds are incorporated to pass even stringent fire tests.

However there are severe disadvantages caused by these chemicals: While antimony oxide is highly toxic and classified as carcinogenic, halogenated organic chemicals have proven to contain significant ecological risks (like bioaccumulation, eco-toxicity, etc.). These traditional flame-retardants can dramatically increase the levels of smoke and toxic decomposition products compared to straight PVC compounds. An example is shown in Figure 1.
450

While Calcium Carbonate as more or less inert filler increases the oxygen index moderately, better efficiency of flame-retardancy is achieved with Aluminium- and Magnesium Hydroxides or Securoc C. Flame-retardancy comes to same level as with Sb2O3. Some research is still underway to use synergistic effects for an improved set of properties at even reduced levels of additives. First results (see Dev. product in Figure 2) already look promising. The use of PVC as a base polymer includes a multitude of very different formulations and properties. The optimal composition for a given application therefore must be adjusted individually. Rigid PVC

400

350

Sm oke Dm

300 0 2 4 6 8 10 p a r ts A n tim o n y O x id e

Most of the flame retarded rigid PVC is used for building materials. As rigid PVC does only contain rather small quantities of flammable substances, the overall fire performance in terms of low flame spread is already excellent. PVC compounds without any further flame retardant additives pass often the standards like the German DIN 4102 (B1, B2) or the French NF P 92-501 (Epiradiateur; M1, M2). For thin parts or films, FR requirements might only be satisfied by adding up to 20 parts of mineral flameretardants, such as the Securoc type. Either these products are used to decrease the level of antimony oxides or to replace it completely. The effect of Securoc C on the Oxygen Index can be taken from Figure 3.
49 Limiting Oxygen Index (%) 48 47 46 45 44 43 42 41 40 0 5 10 15 Parts Securoc C10 20

Figure 1: Antimony trioxide increases smoke level of PVC in a fire1 Using fillers (e.g. Calcium Carbonate) in PVC formulations is state of the art. Application of mineral flameretardants like Portaflame or Securoc leads to PVC based products with high fire performance and good physical properties. Typical plasticized PVC compounds like cable insulation materials usually contain about 50-70 parts of plasticizer, 50-70 parts CaCO3 and 5-8 parts of Sb2O3. Replacement of CaCO3 and Sb2O3 with 70 parts of mineral FRs leads to comparable results in the Oxygen Index Test (ASTM D 2863):
CaCO3 CaCO3/Sb2O3 Securoc C10 ATH MH Dev. Product 0 10 20 30 40

Figure 3: Securoc C in Rigid PVC; Effect on Flame Retardancy The major advantages of Securoc products, besides the reduced flame spread, are: reduced HCl emission, improved temperature stability of the PVC compound, low smoke levels.

Limiting Oxygen Index (%)

Figure 2: Replacement of Antimony Trioxide with different minerals. ASTM D 2863 test results indicate comparable fire performance.
1

Source: A. Chaplin and S.C. Brown from Proceedings Intl. Conference on Fire Safety, New Orleans, March 25-28, 1990; pp. 75-86

Figure 4 shows an example of the described effect for relative smoke density.
10
60 Smoke Density: Obscuration (%) 50

9 8 Output (kg/h) 7 6 5 4 3 2 1 0

non coated coated

40 30 20 10 0 0 5 10 15 20 Parts Securoc C10

20

40 Screw speed (RPM)

60

Figure 4: Rigid PVC: Smoke Density of Compound decreases with increasing level of Securoc C10 (ASTM D 2843) Securoc C10 consists of very fine and regular particles (< 1.0 m, Sedigraph). Their platelet shape, similar to talc, causes improvements in physical properties, e.g. impact strength (see Figure 5). High contents of fillers always require some finetuning of polymer formulations. Here rheology is one of the most critical factors. Viscosity depends very much on quantity and kind of mineral flame retardant used. Generally compound viscosity increases with increasing filler loadings. Finer particles will result in higher viscosity values.
4 Impact Strength (kJ/m2)

Figure 6: Extruder Output: Fatty acid coated Aluminium Hydroxide out rules non coated product2 The more carbonate-like surface properties of Securoc C10 seems to possess better affinity for PVC than straight metal hydroxides, such as ATH. Trials on a small injection-moulding machine show excellent flow behaviour compared to ATH. This can even be improved by surface treatment.

Securoc C10

Coated C10

ATH

3
No filler

10

12

14

16

Flow length (cm)

0 0 5 10 15 20 Parts Securoc C10

Figure 7: Flow length of Rigid PVC compound; comparison of ATH versus Securoc C10 Plasticized PVC Depending on the level and type of plasticizers used, the flammability of plasticized PVC is significantly higher than that of rigid PVC. To achieve the same fire performance much higher quantities of flameretardants must be used. Usually 20 to 25 parts of Securoc (A, B or C respectively) are used to receive

Figure 5: Impact Strength increases with increasing levels of Securoc C10 Besides tailor made particle size distributions surface treatments of fillers represent another possibility to control rheology and processing behaviour. The use of ATH products with fatty acid coatings has been described as state of the art technology to improve extrusion speeds and production output:

source: C. Lffler, Plastverarbeiter 31, (1980) 581

good results. More stringent standards might require up to 50 or 60 parts of the mineral flame-retardants. Correlation between fire performance and filling level is more or less linear (see Figure 8).
HCl emission (mg) 50 45 40 35 30 25 20 15 10 5 0 0 10 20 Filler loading (ppm ) 30

ATH CaCO3

PVC wire and cable formulations contain about 60 to 70 parts of Securoc A or C grades in order to pass usual standards (Limiting Oxygen Index 30 % O2). Combinations with zinc borates (3 - 6 parts) show synergistic effects.
35 Limiting Oxygen Index (%) 30 25 20 15 10 5 0 0 10 20 30 40 50 60 70 Parts Securoc C10 (phr)

40

Figure 10: HCl emission of plasticized PVC3 Modern PVC wire and cable compounds demand a set of good mechanical and electrical properties. Naturally, high loadings of filler type of materials have some negative effect. So tensile strength and elongation at break will show variations, but even with 50 parts of Securoc C10 properties are still within the range of standards.
30 Tensile 25 Tensile strength (MPa) Elongation

Figure 8: Oxygen Index of plasticized PVCcompound correlated to Securoc C10 filling rate All mineral FRs of the Securoc and Portaflame product groups are very effective in reducing the smoke level of PVC in fire tests.
70 Smoke Obscuration (%) 60 50 40 30 20 10 0 0 10 20 30 40 50 60 70 Parts Securoc C10 (phr)

450 400 350 250 200 150 100 50 0

0 10 20 30 40 50 60 Parts Securoc C10 Elongation (%)

20 15 10 5 0

300

Figure 11: Mechanical properties in relation to Securoc C10 loading Performance of PVC compounds in terms of electrical properties is usually excellent. Addition of any type of mineral filler has negative effects on specific resistivity, loss factor etc. Application of ATH still fulfils most European wire and cable standards. Because of its less polar particle surface, Securoc C10 might improve the system as the example in Figure 12 demonstrates.

Figure 9: Smoke Density (ASTM D 2843) in relation to Securoc C filling level Applications requiring reduced levels of HCl emission can also be met by addition of Securoc products. Highly active intermediates formed by these minerals in a fire (test) effectively adsorb acidic gases on the particles surface. The same mechanism is also responsible for smoke reduction.

G. Schnefeld, J. Walter, GAK May 1974, p. 338

No filler

cessability of the PVC plastisol, as long as particles up to 30 microns do not show detrimental effects with respect to surface finish etc. Surface treated grades offer another possibility to make mineral flame-retardants work. Again significant decreases in viscosity can be achieved (see Figure 14).
1000 Coated ATH ATH Viscosity (Pa.s) 1 10 100 1000 100

ATH

Securoc C10

Resistivity (1012 Ohm s.cm )

10

Figure 12: Specific Electrical Resistivity of plasticized PVC compounds PVC Plastisols PVC plastisols are widely used for coatings and related applications. Production technology requires careful rheology adjustment of formulations. Here influence of mineral fillers and flame-retardants gains high importance. Fine fillers raise viscosity more quickly than coarser products, widening the gap with higher filler loadings.

1 0 10 20 30 40 50 60 ATH loading (phr)

Figure 14: Influence of fillers; surface treatment on plastisol viscosity Processing Conditions PVC formulations including FR-fillers can be compounded and processed using the standard equipment. They do not require a change of machinery. Only some processing parameters like temperature, feeding etc. might need some adjustments. Normally typical processing temperatures can be used to run formulations including the Portaflame SG grades. In case, that the temperatures are close to or above 200 C, Securoc B or Securoc C grades offer more flexibility:

1000 2 micron 10 micron Viscosity (Pa.s) 100

10

1 0 10 20 30 40 50 ATH loading (phr)

Grade Portaflame SG Securoc B

Temperature Limit 200 C 320 C 250 C

Figure 13: Viscosity of PVC plastisols as a function of filling rate and median particle size
(Comparison Securoc A5 versus Portaflame SG40)

Securoc C

Besides Securoc C10, Securoc A5 could be used. Where this solution leads to critical viscosities, slightly coarser products like Portaflame SG40 improve pro-

All data and information in this Technical Information are meant as orientation and were given according to our best knowledge. Because properties of compounds and products are widely subject to variations with formulation details, we cannot take responsibility for deviations that might occur in your specific application. We feel committed to our customers needs and would like to give you as much support and help as possible. In order to arrive at quick and satisfying problem solutions detailed discussions with you could be helpful. Therefore we would be glad, if you contact us again for further information.

Ankerpoort N.V. Op de Bos 300 NL 6200 AG Maastricht Telefon: +31 (0) 43 3663755 Telefax: +31 (0) 43 3648272 e-mail: info@ankerpoort.com