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Heat stability and the use of Firebrake ZB ®

in flexible PVC applications
Firebrake® ZB zinc borate is most often used in flexible PVC as a flame retardant synergist
and smoke suppressant – where it can be used alone or in combination with antimony trioxide.

Current reformulation efforts – driven by new fire tests, desire for lower smoke evolution and
with lead-free stabilizers – may require increased attention to the choice of stabilizers for
optimum heat stability. Therefore, a systematic approach must be taken when formulating
PVC compounds with Firebrake ZB, especially for those applications which will be processed at
200 ºC or above and when long residence time during extrusion are expected. Under these
conditions, degradation of PVC caused by “zinc burning” may result in charring, discoloration
or black spots in the melt processed material.

An evaluation was undertaken to determine the optimum choice of commercially available
Ca/Zn and Ba/Zn stabilizers to give good heat stability in the presence of Firebrake ZB and
other typical PVC additives or fillers. Static and dynamic heat stability were evaluated by
degree of discoloration and char formation with respect to time.

Results

Stabilizer Choice
Two Ca/Zn and two Ba/Zn stabilizers were evaluated with 9 phr Firebrake ZB in a basic PVC
formulation and subjected to the static heat stability test at 200 ºC.

Time, minutes at 200 °C + 1 °C
Control 30 35 40 45 50

Ca/Zn Stabilizer 1

Ca/Zn Stabilizer 2

Ba/Zn Stabilizer 1

Ba/Zn Stabilizer 2

For both categories of stabilizers one can clearly observe very significant differences in heat
stability. This illustrates the importance of choosing the right stabilizer in combination with
®
Firebrake ZB when formulating for maximum heat stability.

Their use may be especially beneficial when the use of ESO is not desirable. minutes at 200 °C + 1 °C Control 30 35 40 45 50 Ca/Zn Stabilizer 1 with ESO Ca/Zn Stabilizer 2 with ESO Ba/Zn Stabilizer 1 with ESO Ba/Zn Stabilizer 2 with ESO It is seen that in both Ca/Zn and Ba/Zn stabilized systems the use of ESO can significantly increase the heat stability with respect to time to charring. However. Time. not be desirable for low smoke PVC applications as it tends to increase smoke. Firebrake ZB is again present at 9 phr. however. minutes at 200 °C + 1 °C Control 30 35 40 45 50 Ca/Zn Stabilizer 3 Ca/Zn Stabilizer 3 with ESO Ca/Zn Stabilizer 3 Zeolite/hydrotalcite co-stabilizer . Firebrake ZB was included at 9 phr. In these formulations. It is clear that the effectiveness of ESO will depend on the specific stabilizer system evaluated. An additional improvement in heat stability can be obtained by the use of inorganic co-stabilizers. As in the formulations above. the effect of ESO is compared with that of a zeolite/hydrotalcite co-stabilizer. It may. ESO has little effect on color improvement.Influence of co-stabilizers The use of epoxidized soya bean oil (ESO) can be an option depending on the PVC material properties which are required. Time. These co-stabilizers can help with optimizing the heat stability with respect to both extended time to char and color hold. In these charts.

20 phr MDH . alumina trihydrate (ATH) and magnesium hydroxide (MDH) are often used in PVC wire and cable compounds. Also. From color charts below. 20 phr MDH 4 phr Ca/Zn Stabilizer 1 with ESO 30 phr CaCO3. it is evident that ATH can have a negative effect on heat stability compared to the base system in the presence of zinc borate. minutes at 200 °C + 1 °C Control 30 40 50 55 60 65 70 75 4 phr Ca/Zn Stabilizer 1 30 phr CaCO3. 20 phr ATH 4 phr Ca/Zn Stabilizer 1 30 phr CaCO3. which is used here at 9 phr. one must keep in mind that different grades of these functional fillers may have different effects on heat stability. minutes at 200 °C + 1 °C Control 30 35 40 45 50 4 phr Ca/Zn Stabilizer 1 with ESO 4 phr Ca/Zn Stabilizer 1 30 phr CaCO3 4 phr Ca/Zn Stabilizer 1 30 phr ATH 4 phr Ca/Zn Stabilizer 1 30 phr MDH Heat stability of PVC W&C formulations These color charts show the heat stability performance of typical wire and cable formulations containing 9 phr Firebrake ZB and a preferred Ca/Zn stabilizer. It is seen that good heat stability can be achieved in these formulations without the use of ESO. Influence of fillers and flame retardants Calcium carbonate (CaCO3). Time. This can be important in the development of compounds where low smoke and low rate of heat release are desirable. 20 phr ATH 4 phr Ca/Zn Stabilizer 1 with ESO 30 phr CaCO3. Time.

with ESO 20 phr ATH 6 phr Antimony Oxide 70 75 Conclusions • High heat stability in both static and dynamic testing can be achieved when using effective Borax Asia Pte. as shown in the following examples. Singapore Tel: (65) 738 6068 • When formulating for high heat stability with Firebrake ZB in flexible PVC. 3 phr Antimony Oxide 4 phr Ca/Zn Stabilizer 1 with ESO 20 phr ATH. Ltd. Valencia. 3 phr Firebrake ZB. levels of Firebrake ZB in flexible PVC formulations. California Tel: (1) 800 847 0822 ® (1) 661 287 5780 A member of the Rio Tinto Group Fax: (1) 661 287 5522 . there may be a risk that the original stabilizer used in the antimony-containing formulation is not suitable for the new formulation containing Firebrake ZB. U. reformulation includes the partial or total replacement of antimony trioxide as a synergist. 6 phr Firebrake ZB 4 phr Ca/Zn Stabilizer 1 with ESO 20 phr ATH. minutes at 200 °C + 1 °C Control 30 40 50 55 60 65 70 75 4 phr Ca/Zn Stabilizer 1 with ESO 20 phr ATH. if the stabilizer and other additives have been selected appropriately. there is no reason why the heat stability should not be equal to that of the original antimony formulation. co-stabilizers.com – for more specific advice regarding solving heat stability issues when formulating with Firebrake ZB. Time. the proper choice Fax: (65) 738 6282 of primary stabilizer.boraxfr. Borax Inc. 6 phr Antimony Oxide Dynamic heat 4 phr 5 10 15 20 25 30 35 Ca/Zn Stabilizer 1 stability of PVC with ESO 40 45 50 55 60 65 formulations with 20 phr ATH 6 phr Firebrake ZB antimony trioxide 70 75 80 85 90 and/or Firebrake ZB Dynamic melt stability 5 10 15 20 25 30 35 tests were done on a 4 phr Brabender Plasticorder at Ca/Zn Stabilizer 1 40 45 50 55 60 65 with ESO 200°C and 100rpm. In this case.S. Partial 20 phr ATH and complete antimony 3 phr Firebrake ZB/ 70 75 80 85 90 95 replacement by Firebrake ZB 3 phr Antimony Oxide was evaluated and in both cases the melt stability 5 10 15 20 25 30 35 equals or surpasses that of 4 phr the formulation with Ca/Zn Stabilizer 1 40 45 50 55 60 65 antimony trioxide.Heat stability of PVC formulations with antimony trioxide and/or Firebrake ZB Often. fillers and flame retardant additives is necessary to achieve Borax Europe Limited optimum performance. However. Guildford Please contact the Borax Polymer Additives Group or the distributors listed on our web site – Tel: (44) 1483 242021 Fax: (44) 1483 242099 www.