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.
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. It may, however, not be desirable for low smoke PVC
applications as it tends to increase smoke. As in the formulations above, Firebrake ZB was
included at 9 phr.

Time, 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, ESO has little effect on
color improvement. 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.
In these charts, the effect of ESO is compared with that of a zeolite/hydrotalcite co-stabilizer.
These co-stabilizers can help with optimizing the heat stability with respect to both extended
time to char and color hold. Their use may be especially beneficial when the use of ESO is not
desirable. In these formulations, Firebrake ZB is again present at 9 phr.

Time, 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
 Influence of fillers and flame retardants
Calcium carbonate (CaCO3), alumina trihydrate (ATH) and magnesium hydroxide (MDH) are
often used in PVC wire and cable compounds. From color charts below, it is evident that ATH
can have a negative effect on heat stability compared to the base system in the presence of zinc
borate, which is used here at 9 phr. Also, one must keep in mind that different grades of these
functional fillers may have different effects on heat stability.

Time, 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. This can be important
in the development of compounds where low smoke and low rate of heat release are desirable.

Time, 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, 20 phr MDH

4 phr Ca/Zn Stabilizer 1

with ESO
30 phr CaCO3, 20 phr ATH

4 phr Ca/Zn Stabilizer 1

with ESO
30 phr CaCO3, 20 phr MDH
Heat stability of PVC formulations with antimony trioxide and/or Firebrake ZB
Often, reformulation includes the partial or total replacement of antimony trioxide as a synergist. In this case, 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. However, if the stabilizer and other additives have been selected appropriately, as shown in the following examples,
there is no reason why the heat stability should not be equal to that of the original antimony formulation.

Time, 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, 6 phr Firebrake ZB

4 phr
Ca/Zn Stabilizer 1 with ESO
20 phr ATH, 3 phr Firebrake ZB,
3 phr Antimony Oxide

4 phr
Ca/Zn Stabilizer 1 with ESO
20 phr ATH, 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. 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. 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. Ltd.
levels of Firebrake ZB in flexible PVC formulations. Singapore
Tel: (65) 738 6068
• When formulating for high heat stability with Firebrake ZB in flexible PVC, the proper choice Fax: (65) 738 6282
of primary stabilizer, co-stabilizers, fillers and flame retardant additives is necessary to achieve
Borax Europe Limited
optimum performance.
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.boraxfr.com – for more specific advice regarding solving heat stability issues when
formulating with Firebrake ZB. U.S. Borax Inc.
Valencia, California
Tel: (1) 800 847 0822
®
(1) 661 287 5780
A member of the Rio Tinto Group Fax: (1) 661 287 5522