New formulations and test comparison for the

classification of PVC cables under EU regulation

n° 305/2011 for construction products
Cable 2019: 05-07 March, Düsseldorf, Germany

Gianluca Sarti, Marco Piana

Cable Group Italy
 Cable Group Italy
• The research on new formulations has been performed by Cable Group Italy.
• The group was born in 2013 and it gathers some of the biggest Italian PVC Compounders.
• The aim of the research is the development of new formulations for cables with better
performances in term of flame retardancy, smoke suppressant properties and smoke
acidity.
• The project is called B2ca.

B2ca Project
1 • Evaluation of PVC cables on the market before CPR.

2 • R&D for getting improvements on compounds on lab scale tests.

3 • Evaluation of the new generation of cables.

The target?
• Classification B2ca and the best possible subclasses.
2 B2ca PROJECT
 1 Evaluation of the cables on the market before CPR
As starting point several kinds of CPD cables have been tested with new CPR rules.
FROR: Italian type of cable Insulation: G7 type (HEPR)
N07V-K: Italian type of cable
Bedding: FR PVC based
Jacket: FR PVC Rz type

Insulation: FR PVC R2 type Filler profile

Jacket: FR PVC Rz type FG7OR: Italian type of cable Insulation: FR PVC R2 type

Type Class Smoke Droplets Acidity

FG7OR Dca S2 d1 a3
FROR Cca S2 d0 a3
N07V-K Dca S2 do a3
3 B2ca PROJECT
 2 Lab scale tests
R&D for getting improvements on lab scale tests on specific types of compounds.
We loop over and over again
until we reach the best
compromise.
Match of the properties of
the type of compound and
• Evaluation of flame the processability
retardancy. More than 100
• Evaluation of smoke • Mechanical properties. compounds have been
suppressant properties. • Thermal stability. tested according to the
• Evaluation of the smoke • Insulation properties. following technical
acidity.
• Good processability. standards.
Fire behavior

4 B2ca PROJECT
 2 Lab scale tests
Technical standards performed in term of:
• Fire behavior
• Cone calorimetry (ISO 5660 – 1)
• Oxygen index (ASTM D 2863)
• Smoke Density Rate (ASTM D 2843)
• Smoke acidity (EN 60754 part 1 and 2)

• Type of compound a.t. the technical standard

• Tensile strength & Elongation @ break before and after aging (EN 60811-501,
EN 60811-401, ISO R 527 -1 and -2)
• Water absorption (EN 60811-402)
• Thermal Stability (EN 60811-405)
• Insulation properties
• Other properties a.t. specific technical standard 0f type of
compound 5 B2ca PROJECT
 2 Lab scale tests
Comparison of some critical physical properties
Standard CPD/CPR compound vs next generation compound (NG):

TM1 Jacket CPD Compound CPR Compound Next Generation

Tensile strength [N/mm2] 13,5 13,5 12,5
Elongation @ break [%] 250 250 220
LOI [%O2] 31 34 31
SDR [%] 80 80 50
pH 2,44 2,48 3,86
Conductivity [mS/mm] 151,7 145,7 5,9

6 B2ca PROJECT
 2 Lab scale tests
Comparison of some critical physical properties
Standard CPD/CPR compound vs next generation compound (NG):

90 4,50 160 151,7

80 80 145,7
80 4,00 3,86
140
70 3,50

Conductivity [mS/mm
120
SDR [%]

60 3,00

pH
50 2,44 2,48 100
50 2,50
80
40 2,00
60
30 1,50
20 1,00 40

10 0,50 20 5,9
0 0,00 0
CPD CPR NG CDP CPR NG pH CDP CPR NG Conductivity

SMOKE DENSITY SMOKE ACIDITY

ASTM D 2843 EN 60754 2

7 B2ca PROJECT
3 Tests on cables
Production and classification of the cables
Evaluation of fire performances a.t. CPR. Standard performed:

• EN 60332-1-2 (Vertical flame propagation on single cable)

• EN 50399 (Vertical flame propagation on bunched cables)
• EN 61034-2 (Smoke density in 27 m3 chamber)
• EN 60754-2 (Test on gases evolved during combustion of materials from cables )
• Part 2: Determination of acidity (by pH measurement and conductivity)

8 B2ca PROJECT
 3 Tests on cables
Production and classification of the cables

• All tests
• Identification of Classes
required by
Tests a.t. CPR • B2ca, Cca, Dca, Eca or Fca
specific
standard of • THR, HRR, FIGRA, FS, SPR : EN 50399 • Identification of Subclasses
the cable • TSP, SPR: EN 61034-2 • S1a, S1b, S2, S3
• Processability • Flaming Droplets: EN 50399 • d0, d1, d2
• Smoke acidity: EN 60754-2 • a1, a2, a3

Match of cables’ Classification of the cable

characteristics a.t.
specific standard.

9 B2ca PROJECT
 3 Tests on cables: what we did
Performances: CPD vs CPR cables
CPR Cables Class Smoke Droplets Acidity

FG16OR16 Cca S2 d0 a3

FROR B2ca S2 d0 a3

FS17 Cca S1 do a3

CDP Cables Class Smoke Droplets Acidity

FG7OR Dca S2 d1 a3

FROR Cca S2 d0 a3

N07V-K Dca S2 do a3

10 B2ca PROJECT
 3 Tests on cables: next plan
Performances:
Comparison b/wCPR vs New
old and newGeneration
cables cables
Next step will be the evaluation of cables with new compounds

New Cables Class Smoke Droplets Acidity

FG16OR16 B2Ca S1 d0 a2

CPR Cables Class Smoke Droplets Acidity

FG16OR16 Cca S2 d0 a3

But the most difficult task will be the reduction of smoke acidity

11 B2ca PROJECT
FOCUS ON SMOKE ACIDITY
Technical standards a.t. CPR
EN 60754-2
• Tubular Oven at fixed temperature ranging b/w 935°C up to 960°C
• Determination of pH and conductivity
• Requirements 1 for class a2: pH > 4,3, Conductivity [mS/mm] < 10
• Requirements 2 for class a1: pH > 4,3, Conductivity [mS/mm] < 2,5
• The requirement 1 defines what is an Halogen Free

The method used 4 PVC before CPR

EN 60754-1
• Tubular Oven at temperature ranging b/w 790°C up to 810°C
• Temperature regime
• Determination of mg of halogens in 1 g of compound
12 FOCUS ON SMOKE ACIDITY
ACID SCAVENGING THEORY
°C

EN 60754/1
Acid scavengers RXN prod. stable@ 810°C

Pyrolysis
&Combustion
Thermal
Zone
Stabilization Massive release of
Uncharted Zone
Zone HCl generally
described by a two
stages pyrolysis
model [1],[2]
EN 60754/2
Acid scavengers RXN prod. stable@ 960°C

13 FOCUS ON SMOKE ACIDITY

 Single vs Multiple Step reaction
• Single step reaction: Z is stable up to pyrolysis zone and it creates Z-Cl stable up to the test temperature.
• Multiple step reaction: A, stable up to pyrolysis zone, reacts with HCl giving A-Cl; A-Cl decomposes but a
«team mate» is ready to get the HCl and so on up to the test temperature (relay race scheme).
°C

Thermal Stabilization Pyrolysis & Combustion Uncharted Zone

Zone Zone

Z Z-Cl

C-Cl

B-Cl

A A-Cl

14 FOCUS ON SMOKE ACIDITY

Multiple Step vs Single Step reaction
• Failure case 1: W-Cl decomposes making free HCl before reaching the test temperature.
• Failure case 2: D-Cl decomposes making free HCl before the formation of E.
• Failure case 3: The Acid Scavengers are too slow in getting HCl in (Kinetic problem).
°C

Thermal Stabilization Pyrolysis & Combustion Uncharted Zone

Zone Zone

W W-Cl W + HCl

D D-Cl D +HCl

15 FOCUS ON SMOKE ACIDITY

Acid scavenging theory: inert substance
• Al(OH)3 starts the decompositions b/w 180°C and 200°C, releasing water. It acts as heat sink,
it dilutes the flame, it dilutes the polymer and plasticizers, it creates a char of Al2O3 [3].
• From acid scavenging point of view Al(OH)3 is useless due to its chemical inertia.
°C

Thermal Stabilization Pyrolysis & Combustion Uncharted Zone

Zone Zone

Al(OH)3 / Al2O3 Al2O3 + HCl

RM phr
PVC S K70 100 LOI 28 [%O2]
Al(OH)3 80 pH 2,22
DINP 50 Conductivity 212 mS/mm
STAB 5

16 FOCUS ON SMOKE ACIDITY

Acid scavenging theory: ineffective substance
• Mg(OH)2 starts the decompositions b/w 300°C and 320°C, releasing water. It acts as heat
sink, it dilutes the flame, it dilutes the polymer and plasticizers [3].
• From acid scavenging point of view in a single step reaction Mg(OH)2 is ineffective due to the
instability of its reaction product [4].
°C

Thermal Stabilization Pyrolysis & Combustion Uncharted Zone

Zone Zone

Mg(OH)2 / MgO MgCl2 MgO + HCl

RM phr
PVC S K70 100 LOI 28 [%O2]
Mg(OH)2 80 pH 2,27
DINP 50 Conductivity 188 mS/mm
STAB 5

17 FOCUS ON SMOKE ACIDITY

Acid scavenging theory: good acid scavenger
• AS6 is stable along the pyrolysis and combustion zone and it reacts efficiently with HCl,
trapping it in a reaction product.
• Its reaction product is stable up to the maximum temperature required by EN 60754-2.
• But we need to enhance the AS6 concentration to compensate the low efficiency.
°C

Thermal Stabilization Pyrolysis & Combustion Uncharted Zone

Zone Zone

AS6 AS6-Cl

RM phr
PVC S K70 100 LOI 25 [%O2]
AS6 120 pH 3,98
DINP 50 Conductivity 4,4 mS/mm
STAB 5

18 FOCUS ON SMOKE ACIDITY

 But what happens to the flame retardancy?

If most of HCl is RM
PVC S K70
phr
100
scavenged, CaCO3 90
the intrinsic MDH (Mg(OH)2 0
flame DINP 50
STAB 5
retardancy of
ATO (Sb2O3) 0
PVC is
pH 2,59
switched off Conductivity 107,2 mS/mm
LOI 23 %O2

19 19
FOCUS ON SMOKE ACIDITY
FOCUS ON SMOKE ACIDITY
But what happens to the flame retardancy?
• Sb2O3 works totally in gas phase. Sb2O3 creates SbCl3 acting as a “quencher” of radicals feeding
the flame.[5] But AS-1B scavenges all HCl, and Oxygen Index drops down to 23 %O2.
• Even if we double the Sb2O3 quantity we have no effect at all.
RM phr RM phr RM phr
PVC S K70 100 PVC S K70 100 PVC S K70 100
CaCO3 60 AS-1B 123 AS-1B 123
MDH 30 MDH 30 MDH 30
DINP 50 DINP 50 DINP 50
Stabilizer 5 Stabilizer 5 Stabilizer 5
ATO 5 ATO 5 ATO 10
pH 2,63 pH 4,12 pH 4,03
Conductivity 99,3 mS/mm Conductivity 3,20 mS/mm Conductivity 4,00 mS/mm
LOI 32 %O2 LOI 23 %O2 LOI 23 %O2
20
20 FOCUS
FOCUSON
ONSMOKE
SMOKEACIDITY
ACIDITY
But what happens to the flame retardancy?
Sb2O3 (cond.) + 6HCl (gas) -----------> 2SbCl3 (gas) + 3H2O (v)

SbCl3 + H*  HCl + SbCl2*

SbCl2 + H*  HCl + SbCl* Complete inhibition of the
SbCl + H*  HCl + Sb* quenching of the «hot radicals»
Sb* + OH*  SbOH feeding the flame and flame
SbOH* + H*  SbO* +H2 retardancy drops down.
SbO* + H*  SbOH

In absence of AS-1B we have the formation of SbCl3 and the quenching mechanism is active.

AS-1B prevents the formation of SbCl3.

21
21 FOCUS
FOCUSON
ONSMOKE
SMOKEACIDITY
ACIDITY
But what happens to the flame retardancy?
• Ammonium Octamolybdate (AOM) works mainly in condensed phase: decomposes b/w 287 °C and
370 °C to MoO3 [6] ; it reacts with HCl creating MoO2Cl2 a powerful Lewis acid promoting the
formation of a char barrier between gas and condensed phase[7],[8].
• AS-1B, interfering with the char creation mechanism of AOM, inhibits totally its flame retardancy.
RM phr RM phr RM phr
PVC S K70 100 PVC S K70 100 PVC S K70 100
CaCO3 60 AS-1B 123 AS-1B 123
AOM 30 AOM 30 AOM 53
DINP 50 DINP 50 DINP 50
Stabilizer 5 Stabilizer 5 Stabilizer 5
ATO 3 ATO 3 ATO 3
pH 2,43 pH 4,13 pH 4,08
Conductivity 155,2 ms/mm Conductivity 2,88 ms/mm Conductivity 3,12 ms/mm
LOI 38 %O2 LOI 23 %O2 LOI 24 %O2
22
22 FOCUS
FOCUSON
ONSMOKE
SMOKEACIDITY
ACIDITY
But what happens to the flame retardancy?
• The only way to recover flame retardancy is the reduction of AS-1B.

• So we need other routes for getting back the lost flame retardancy.

RM phr RM phr RM phr

PVC K70 100 PVC K70 100 PVC K70 100
AS-1B 123 AS-1B 100 AS-1B 60
AOM 30 AOM 53 AOM 53
DINP 50 DINP 50 DINP 50
Stabilizer 5 Stabilizer 5 Stabilizer 5
ATO 3 ATO 3 ATO 3
pH 4,13 pH 3,05 pH 2,76
Conductivity 2,88 ms/mm Conductivity 37,8 ms/mm Conductivity 72,9 ms/mm
LOI 23 %O2 LOI 26 %O2 LOI 32 %O2
23
23 FOCUS
FOCUSON
ONSMOKE
SMOKEACIDITY
ACIDITY
 Advantages
Focus on technical standards used “800 °C“ ensure a higher number
of stable substances.

EN 60754-1: used before CPR We can use easily multiple

steps reactions, enhancing
synergism b/w substances.
With a temperature ramp acid
scavengers have more time to
trap the evolving HCl.

In term of temperature and

ramp it is more similar to a real
From 23°C to 800 +/-10 °C @ 20°/min
fire scenario. 24
FOCUS ON SMOKE ACIDITY
 Disadvantages
Focus on technical standards used A higher temperature gives a
smaller number of stable
substances.
EN 60754-2: a.t. CPR The decomposition makes free
HCl again.
Without temperature ramps
acid scavengers have no time to
trap the evolving HCl
efficiently.

Fixed b/w 935°C and 960°C 25

25 FOCUS ON SMOKE ACIDITY
Differences in numbers
• We tested the same compound with the two standards EN60754-1 and EN 60754-2.
• The EN60754-1 is performed with its temperature regime and 800°C as final temperature, but,
instead of the mgs of halogens in 1 gram of compound, pH and Conductivity are measured.
• That to permit a comparison b/w EN 60754-1 and EN 60754-2, focusing on the effect of the
ramp and the final temperature on data’s.
• In all tests the EN 60754-1 gives higher values of pH e lower values of conductivity. The gap
depends on the mechanism of action of used acid scavengers and on the presence of
sources of labile Cl.
2 EN 60754 part 2 EN 60754 part 1
Formulation pH Conductivity H+ pH Conductivity H+
Code [mS/mm] [mol/L] [mS/mm] [mol/L]
54 3,54 10,4 2,88 x 10-4 4,00 3,80 1,00 x 10-4
90 3,75 7,10 1,78 x 10-4 4,24 3,00 5,75 x 10-5
91 2,46 140,0 3,47 x 10-3 2,65 90,4 2,24 x 10-3
94 3,52 13,5 3,02 x 10-4 4,07 3,90 8,51 x 10-5

26
26 FOCUS ON SMOKE ACIDITY
Relationship b/w pH and conductivity
In in the bubbling devices the stronger electrolyte is always HCl.
Pyrolysis and combustion of PVC jackets by TGA/FTIR shows the main presence of HCl, CO2 and H2O[2].
Conductivity [pH] Measured vs Expected Conductivity
Nonlinear regression 450

Experimental data's Model 400

Measured Conductivity in micro S/mm

450 350
400
300
Conductivity in micro S/mm

350
300 250

250 C=ax 10-b x pH 200

200 150
150
100
100
50
50
0 0
1 2 3 4 5 6 7 0 50 100 150 200 250 300 350 400 450
pH Expected Conductivity in micro S/mm)

So no other volatile substance can affect conductivity driven only by the presence of HCl.
27
27 FOCUS ON SMOKE ACIDITY
Conclusions: why PVC Cables[9]
• PVC can obtain the highest fire reaction results compared with any thermoplastic material:
it can reach the Euroclass B-s1-d0;
• PVC is self-extinguishing and has intrinsically a high potential to resist ignition sources: it does not
contribute, or only minimally contributes, to the generation and spread of a fire;
• PVC irradiates only a minimum amount of heat; this means a minimum contribution to heat
diffusion;
• Hydrogen Chloride (HCl) contained in the smoke is highly irritating but provides an immediate
signal of the development of the fire, acting as an escape alarm;
• No irreversible damage to the building structure can be caused by the release of hydrogen
chloride in the event of a fire.

Thank you for your attention

Thanks to: • Cable Group Italy
• PVC Forum Italia www.pvcforum.it

• PVC4cables www.pvc4cables.org
28 CONCLUSIONS
CONCLUSIONS
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References
[1] Wu, C.-H., et al. Two-Stage Pyrolysis Model of PVC. [8] W. H. Starnes Jr., L. D. Wescott Jr., W. D. Reents Jr., R. E. Cais, G. M. Villacorta, I. M. Plitz,
Canadian J. Chem. Eng.: Aug 1994, 72(4), 644-650. L. J. Anthony. Mechanism of Poly(Vinyl Chloride) Fire Retardance by Molybdenum(VI)
https://doi.org/10.1002/cjce.5450720414. Oxide. Further Evidence in Favor of the Lewis Acid Theory. Polymer Additives, J.E. Kresta,
Ed., Plenum Press, New York and London, 1984, 237.
[2] Zhi Wang, Ruichao Wei, Wang Xuehui , Junjiang He, and Jian Wang. Pyrolysis
https://doi.org/10.1007/978-1-4613-2797-4_18.
and Combustion of Polyvinyl Chloride (PVC) Sheath for New and Aged Cables
via Thermogravimetric Analysis-Fourier Transform Infrared (TG-FTIR) and
Calorimeter. Materials (Basel), Oct 2018, 11(10), 1997.
https://doi.org/10.3390/ma11101997.
[9] CPR-PVC CABLES:
[3] Richard Hull, Artur Witkowski, Luke Hollingbery.
PVC4CABLES
Fire retardant action of mineral fillers.
www.pvc4cables.org
Polymer degradation and Stability, Aug 2011, 96 (8), 1462-1469.
https://doi.org/10.1016/j.polymdegradstab.2011.05.006.
[4] G. J. Kipouros, Donald R. Sadoway. A Thermal Analysis of the Production
of Anhydrous MgCl2. Journal of Light Metals, May 2001, 1(2),111-117.
https://doi.org/10.1016/S1471-5317(01)00004-9.
[5] Fouad Laoutid, Leila Bonnaud, Michael Alexandre, J-M. Lopez-Cuesta,and
Philippe Dubois. New prospects in flame retardant polymer materials: from
fundamentals to nanocomposites. Material Science and Engineering Reports,
Jan 2009, 63(3), 100-125.
https://doi.org/10.1016/j.mser.2008.09.002.
[6] Eikoh Ma. The Thermal Decomposition of Ammonium Polymolybdates.
II. Bulletin of the Chemical Society of Japan, Jan 1964, 37(5), 648-653.
https://doi.org/10.1246/bcsj.37.648.
[7] W.-K. Ho, J.K. Walker, S.V. Orski, T.W. Fuller, A.G. Zestos, C.L. Grinnell, R.D.
Pike, W.H. Starnes Jr. A New Synergistic Effect in the Smoke Suppression of
Plasticized Poly(vinyl chloride) by Mixed-Metal Cu(II) Oxides. Journal of
Vinyl and Additive Technology, Mar 2008, 14(1), 16-20.
https://doi.org/10.1002/vnl.20139.

29 CONCLUSIONS