Lead-Free Stabilization For PVC Pipes: The New Alternative

Mrs Muriel Hebrard

ROHM AND HAAS EUROPE SERVICES ApS Valbonne - France

Dr. Eric G. Lundquist, Dr. Jian-Yang Cho

ROHM AND HAAS COMPANY Spring House - USA

ABSTRACT

With its outstanding cost performance benefits, PVC remains the material of choice for the
construction industry and pipe producers. However, environmental concerns and regulations will
lead to the elimination of lead based heat stabilizers over the next five years. This move to lead free
stabilizers currently forces pipe producers to re-evaluate their stabilizer options as they strive to
keep the cost competitiveness of their PVC formulations. Thus, the challenge for stabilizer
manufacturers is to propose new lead-free stabilizers for pipes with good performance and
attractive costs.
Rohm and Haas Company has developed a new stabilization system that is based on a derivative
of the mercaptan chemistry which has been used for decades with conventional tin stabilizers. The
patented technology includes organic based, heavy metal free compositions that contain blocked
thiols, which under vinyl processing conditions generate highly active stabilizing components.
These innovative systems offer wide processing windows, give excellent early color, and can be
adjusted to meet the various technical requirements of the pipe market. The stabilizing systems are
odor free, and are compatible with all standard stabilizer systems. Additional benefits include
reduced cross-linking leading to easier recycling. These new stabilizing systems are non toxic,
contain no heavy metals, and are available as stabilizer additives or as one-packs, offering
excellent price/performance ratio. Considering these technical benefits as well as the conclusions of
a stabilizer sustainability assessment, this new technology represents an advanced and more
sustainable solution for PVC pipes stabilization.
The present article details the stabilization mechanism and performance attributes (stabilization,
rheology, and recycling data) on both laboratory and industrial equipment of this new lead-free PVC
stabilizer.

INTRODUCTION

The use of plastics pipes in the European pipe market has continued to increase and represents a
majority position today capturing about 54% of the total pipe used [1]. Among all plastics materials
used for pipes, PVC remains the material of choice accounting for approximately two thirds of the
European pipe market [2].

Table 1: ER PVC pipe market [3]

PVC market PVC Pipe production Plastics pipe production

(kt) (kt) (kt)
Western Europe 5625 1365
Eastern Europe 1120 225
Total 6745 1590 2500

Within the PVC pipe market, lead based heat stabilizers are still the most widely used heat
stabilizer accounting for nearly 50% of the worldwide volume. In fact, lead based stabilizers
dominate the PVC stabilizer market in all regions except the North American, where lead stabilizers
were phased out in the 1970’s and tin stabilizers predominant.
 100%

90%

80%

70%

60%

50%

40%

30%

20%

10%

0%
Asia-Pacific Europe North America Rest of the world

Lead Mixed metals Organotin Organic

Figure 1: Stabilizer use in world market [4]

In North America, tin based stabilizers will probably continue to dominate the PVC pipe market. In
Europe however, environmental concerns and regulatory issues will push for the elimination of lead
based heat stabilizers over the next five years. European heat stabilizer manufacturers have made
a voluntary commitment, called Vinyl 2010, to achieve a 50% reduction in lead stabilizer use by
2010 and to be lead-free by 2015. This commitment also applies to the plastic pipes and fittings
industry represented by TEPPFA. TEPPFA calls for a phase out of lead stabilisers in the EU for
pipes and fittings made of virgin PVC targeting 25% reduction in 2005, 75% in 2010 and 100% in
2015.
The Asian market as well as the rest of the world is expected to follow the European commitment
with a progressive elimination of the lead-based stabilizers.

120

105

90

75
kTons

60

45

30

15

0
2000 2005 2006

Lead Mix metals & organic Organotin

Figure 2: General consumption of PVC stabilizers

(sales in 15 EU countries plus Norway, Switzerland and Turkey) [5]

With a decrease of more than 20% over the last 6 years, the PVC lead stabiliser substitution in
Europe is indeed progressing.
This move to lead free stabilizers will cause pipe producers to re-evaluate their stabilizer options as
they strive to keep the cost competitiveness of their PVC formulations. Thus, the challenge for
stabilizer manufacturers is to propose new lead-free stabilizers for pipes with good performance
and attractive costs.
CaZn stabilizers are already proposed as alternatives to lead-based stabilizers for pipe applications.
However, the performance/price ratio of CaZn stabilizers has often not been viewed as being
attractive enough to accelerate the phase-out of lead stabilizers before regulations mandate a total
change.
 40

35

30

25

kTons
20

15

10

0
2003 2006

Lead Mix metals & organic

Figure 3: Lead replacement in PVC pipe application (EU) – ESPA estimate [6]

In an effort to produce an alternative to lead stabilizers and to overcome the deficiencies associated
with traditional CaZn stabilizers, the Rohm and Haas Company has developed a new system,
AdvapackTM NEO Heat Stabilizer, that is based on a derivative of the mercaptan chemistry which
has been used for decades with conventional tin mercaptide stabilizers. This patented technology
includes organic based, heavy metal free compositions that contain blocked thiols, which under
vinyl processing conditions, generate highly active stabilizing components.

THE BLOCKED THIOL TECHNOLOGY

Poly(vinyl chloride) (PVC), one of the oldest thermoplastics, undergoes severe degradation under
the conditions of heat and shear used to process it. To remedy this, heat stabilizers have been
developed and must be used in all PVC processing applications. Lead and tin based heat
stabilizers are the most utilized of the PVC thermal stabilizers and their mode of stabilization has
been deeply studied.
With Tin mercaptides, the stabilization mechanism involves a reaction in which the mercaptan
moiety of the tin based stabilizer adds to the defective site on the PVC backbone and the labile
chloride is removed as a tin chloride. Fundamental work on this mercaptan reaction mechanism
clearly shows the ability of generated free mercaptans to act as efficient PVC heat stabilizers.
Unfortunately, such free mercaptans can create an offensive odor and are non-compatible with lead
based stabilizers causing cross–staining reactions.
To overcome these issues, Rohm and Haas has developed patented technology based on the idea
that the mercaptan should not be free but linked to an organic molecule acting as blocking moiety to
suppress the adverse effects of the free mercaptan. The resulting block thiol or latent mercaptan
technology is free from the mercaptan odor and does not cross- stain with lead.

S S S
Sn R H R B R

Tin mercaptides Free mercaptans Blocked thiols

( B: organic moiety)
Figure 4: Blocked thiols
During processing of the PVC formulation, shear and temperatures induce the generation of highly
active stabilizing components that immediately react with the PVC chain. The release of the active
mercaptan is a concerted mechanism involving the blocked thiol [7, 8, 9, 10]. In addition to the
substitution of the labile chlorines, other specific stabilization mechanisms also occur and are
responsible for delaying the cross-linking phenomena.

S
∆Η
B R
PVC processing
Blocked thiols Cl Cl Cl SR
(B: organic moiety) S
B R

Figure 5: The blocked thiols stabilization mechanism

ILLUSTRATION OF THE NEW LEAD-FREE TECHNOLOGY PERFORMANCE

1/ Laboratory testing: heat stabilization and rheology

AdvapackTM NEO Heat Stabilizer is compared to high performance commercial lead or CaZn one-
pack systems. The basic compact pipe formulation includes Suspension PVC EVIPOL K68 (100
parts), TiO2 KRONOS CL2220 (0.2phr), and CaCO3 OMYALITE 95T (2phr).
All the tested dry-blends have been prepared on high speed mixers - HENSCHEL and PLASMEC –
under similar conditions with a maximum temperature of 110°C. Rheology and stabilizing efficiency
of the different one-packs have been evaluated on a Brabender rheometer Plasticoder PL-200 and
a Collin 150 two-roll mill, through torque curves, dynamic thermal stability curves, color on
calendered films, and static stability test on the films.

Table 2: Conditions and settings for laboratory tests

Dynamic thermal stability: Collin 2-roll mill 200°C , 180g dry-blend

Calendered films: Collin 2-roll mill 200°C, 3 minut es, 180g dry-blend
Static Stability: Metrastat oven 205°C, 12 min pre- heating, 30 min heating
Brabender rheometer 190°C, 60rpm, 6min, 65g dry-ble nd
Color properties Colorimeter "HUNTERLAB" DP-9000 - CIE lab 1976.

Figure 6: Dynamic stability test on the two-roll mill clearly demonstrates that AdvapackTM NEO Heat
Stabilizer has significantly better color hold than the tested CaZn commercial one-pack. While the
yellow index is progressively increasing since the beginning of the test with the CaZn, the
AdvapackTM NEO formulation has very stable YI value. The lead one-pack performances are much
poorer in terms of initial and mid term color, but the long term stability is superior.

Yellow Index
84
80
76
72
68
64
60
NEO 1110
56
52 CaZn one-pack 1
48
44
40
Pb one-pack 1
36
32
28
24
20
16
12
8
4
0
120 240 360 480 600 720 840 960 1080 1200
Milling time (sec)

Figure 6: Dynamic thermal stability on Collin 2-roll mill (200°C)

TM
Advapack NEO 1110 (2.35 phr) – CaZn commercial one-pack 1 (2.2 phr) - Lead one-pack 1 (2.8 phr)
Figure 7: The color (b* index) measured on calendered films confirm that the lead stabilized system
has poor initial color and is most probably designed for pigmented pipe applications. Color on films
is much less yellow with non lead based one-pack systems, with even lower b* for AdvapackTM
NEO. Even though pigmented applications do not require outstanding initial color, it is still better to
have a color advantage as seen with AdvapackTM NEO. In fact most of the modifications to increase
long term heat stability, in particular for bigger diameters pipes, impact the early color and increase
the yellowness.

b* on films

24
23
22
21
20
19
18
17
16
15
14
13
12
11
10
NEO 1110 CaZn one-pack 1 Pb one-pack 1

Figure 7: Color on calendered films (b*)

TM
Advapack NEO 1110 (2.35 phr) - CaZn commercial one-pack 1 (2.2 phr) - Lead one-pack 1 (2.8 phr)

Figure 8 and 9: In Brabender tests measuring fusion time, the CaZn one-pack demonstrates much
slower fusion than the reference lead system. AdvapackTM NEO system has been designed to be
much closer to standard lead systems in terms of rheological behaviour such as fusion time and
torque curves. In addition, having faster fusion with still good thermal stability, rather than too slow
fusion, allows for easier rheological adjustment when required.

Torque (Nm)
Fusion time (sec)
80 100
90 NEO 1110
70
80
60 CaZn one-pack 1
70
50 60 Pb one-pack 1
50
40
40
30
30
20 20
10
10
0
0 0 30 60 90 120 150 180 210 240 270 300 330 360
NEO 1110 CaZn one-pack 1 Pb one-pack 1 Time (sec)

Figure 8: Fusion time Figure 9: Torque curves

Figures 7, 8, 9: data from rheology testing on Brabender rheometer

TM
Advapack NEO 1110 (2.35 phr) - CaZn commercial one-pack 1 (2.2 phr) - Lead one-pack 1 (2.8 phr)

2/ Pipe extrusion data

Pipe extrusions have been run on a variety of different size Bausano extruders, comparing
AdvapackTM NEO grades to lead, CaZn and tin stabilized formulations. The amount of filler varied
from 5phr up to 50phr to cover applications from pressure pipes to standard building pipes.

2.1/ Laboratory extruder Bausano MD2 / 46B20-A

This Bausano extruder is a 46mm and 20D counter rotating parallel twin screw extruder. Extruded
pipes have a diameter of 60 mm and 2 mm thickness. The extruded formulations include
Suspension PVC EVIPOL K68 (100 parts), TiO2 KRONOS CL2220 (0.2phr), and CaCO3
OMYALITE 95T (2phr).
 Table 3: Extrusion on Bausano MD2/46B20-A

Temp set/act (zones/°C)

Torque
Back P

Melt T
Screw
Extrusion #1

rpm

Nm
bar

°C
1 2 3 4 5 6 7
180 180 182 185 185 193 198
NEO 1110 (2.35 phr) 34 165 294 191 179 180 181 184 184 193 198
CaZn OP2 (2.5phr) 34 170 305 190 177 180 182 185 188 196 202

Temp set/act (zones/°C)

Torque
Back P

Melt T
Screw
Extrusion #2
rpm

Nm
bar

°C
1 2 3 4 5 6 7
180 182 185 185 188 195 200 L* a* b*
NEO 1210 (2.54phr) 30 195 286 192 187 185 187 191 195 198 201 88.2 -0.6 10.4
CaZn OP3 (2.5phr) 27 225 318 190 185 185 184 190 192 196 200 85.7 -2.9 18.0

Table 3: In experiments comparing AdvapackTM NEO one-packs to commercial CaZn systems

under similar extrusion conditions, AdvapackTM NEO systems demonstrate lower melt-pressure.
Further extrusion trials have shown that this lower melt pressure allows for significantly increased
output rates. Regarding color on extruded pipes, AdvapackTM NEO 1210 demonstrates excellent
early color, in particular regarding a* and b* values, and thus brings technical advantage for white
pipes and clear colour applications.
Figure 10: Considering residual stability on extruded pipes, static heat stability tests have been
performed on the pipe samples, using a Metrastat static oven. The color change curves show that
AdvapackTM NEO provides better mid-term color hold than the tested commercial CaZn systems.
This is a technical benefit when considering processing window and residence time variations that
occur during industrial extrusions.

Delta E
20

18

16 NEO 1110 (2.35phr)

14
CaZn OP2 (2.50phr)
12

10

0
0 120 240 360 480 600 720 840 960 1080 1200 1320 1440
Time (sec)

Figure 10: Residual static stability test on pipes – Metrastat oven

2.2/ Industrial extruder Cincinnati CMT45 twin conical screws

Extrusion of pressure pipes (according to European standard EN 1452-2) with a diameter of 63mm
and 2.5mm thickness. The extruded formulations include Suspension PVC K67 (100 parts), CaCO3
OMYA 50H (4phr), and grey pigmented masterbatch. AdvapackTM NEO 1110 one-pack dosage is
2.45phr, CaZn commercial one-pack 4 dosage is 2.6phr.

Table 4: Extrusion on Cincinnati CMT 45

Gelation
Torque
Mass P

Pulling

Temp set/act (zones/°C)

Melt T

Congo
m/min
Screw

Gloss
Vicat

DSC

Red
rpm

60°
bar

°C
%

1 2 3 Die
NEO 1110 (2.45 phr) 36 169 70 3.5 180 170 160 180/180/200/200 > 80°C 24 77% 181 t + 25%
CaZn OP4 (2.6phr) 36 178 68 3.3 180 170 160 180/180/200/200 > 80°C 20 67% 180 t
Output rate # 150 kg/hr.
AdvapackTM NEO 1110 shows close rheology compared to the commercial CaZn, but with lower
mass pressure. Superior gelation level is achieved on AdvapackTM NEO 1110 pipes. Pulling speed
is higher with NEO, and output rate could be increased further more considering the lower melt
pressure (setting higher screw speed). Both pipes have very nice aspect and overall good
properties. Pipes including AdvapackTM NEO 1110 have higher residual stability.

2.3/ Industrial extruder Bausano MD2 / 72/24

This Bausano extruder is a 72mm and 24D counter rotating parallel twin screw extruder, with screw
thermo-control. Extruded pipes have a diameter of 114 mm and 5 mm thickness.
The extruded formulations include Suspension PVC K67 ETINOX (100 parts), TiO2 KRONOS
CL2220 (0.5phr), carbon black (0.03phr) and CaCO3 OMYA 2T-AV (5, 16, 50phr). AdvapackTM NEO
1110 one-pack dosage is 2.35phr. For pipe formulations with high amount of filler, additional
external lubricant is added. AdvalubeTM C-109 was used. (0.2phr with CaCO3 at 16phr / 0.6phr with
CaCO3 at 50phr).

Table 5: Extrusion on Bausano MD2/72/24

DB bulk

Screw T

Output
density

Back P
Extruder zones (set/let) °C Head zones (set/let) °C Die

Screw

Amps

kg/hr
CaCO3

(°C)

rpm

bar
(phr)
1 2 3 4 5 6 7 8 9 °C
Vent

5 0.615 170/169 180/179 190/190 175/170 165/170 175/175 185/185 185/196 185/190 190/190 135 40 135 41 195
16 0.369 170/170 180/179 190/190 175/181 170/172 180/179 190/189 190/191 190/189 195/194 140 40 100 35 202
50 0.737 170/169 180/179 190/189 175/179 170/173 180/180 190/189 190/193 190/189 195/193 140 40 180 35 230
Gelation

Color on grey

density
Gloss

Vicat
CaCO3
Pipe
60°

Stabilizer pipes
(phr)
L* a* b*
5 46.2 -0.6 -1.5 40 94 1.32
NEO 1110 16 47.0 -0.6 -1.0 20 81 1.35
> 80°C
50 48.2 -0.2 0.9 20 81 1.57
Pb 40 orange pipes 8 84 1.45

Formulations with 5, 16 and 50phr of filler have been extruded using similar settings. All pipes had
immediate correct and stable dimensions (no thickness variations), showing good melt flow
properties. Output rates from 200kg to 230kg/hr were achieved. Good gelation levels were obtained
even for the formulations containing 50phr of calcium carbonate filler. Even at the highest filler
levels, the AdvapackTM NEO stabilized pipes demonstrate significantly higher gloss than the lead
pipe reference.

ENHANCED RECYCLING PROPERTIES FOR PVC PIPES

The recycling of PVC pipes is important to maintaining the environmental and financial sustainability
of PVC. In 2006, PVC recycling in Europe doubled again and the European plastic pipe industry
represented by TEPPFA continues to push for even more recycling of pipe products in the coming
year [11].
The use of recycled PVC materials can lead to several complications including color variation and
rheological difficulties due to advanced decomposition of PVC.
To evaluate stabilizer impact on the ability for recycling, PVC pipe formulations were processed,
ground and re-processed several times, using either 100% recycled material or 20% recycled
material mixed with 80% fresh-dry-blend. The AdvapackTM NEO system has been compared to a
commercial CaZn one-pack. The impact on rheology and color has been evaluated under the test
conditions presented in Table 2.
 17
16

16 14
Fresh dry-blend

Delta fusion torque (Nm)

15 12
100% recycled
100% Recycled
Color on films (b*)
14 10

13
8
12
6
11
4
10
2 Cycle Cycle Cycle Cycle Cycle Cycle
9 I II III I II III

0
8
NEO 1110 Ca Zn One-pack 2
NEO 1110 Ca Zn One-pack 2

Figure 11: Color on calendered films Figure 12: Difference of fusion torque
after 1 to 3 recycling cycles using 100% recycled

110
105 226
100 225
95 Ca Zn One-pack 2
224

Equilibrium temperature (°C)

90
223
Fusion time (s)

85
222
NEO 1110
80
75 Ca Zn One-pack 2 221
70 220
65 NEO 1110 219
60
218
55
50 217
45 216
40 215
0 1 2 3 4 5 6 7 0 1 2 3 4
Recycling cycles (20%) Recycling cycles (100%)

Figure 13: Fusion time Figure 14: Equilibrium temperature

st th st th
from 1 to 7 recycling cycle using 20% recycled from 1 to 4 recycling cycle using 100% recycled

TM
Figures 11 to 14: Brabender rheology - Advapack NEO (2.35 phr) - CaZn commercial one-pack 2 (2.5 phr)

Figure 11: This comparison shows that even after recycling, excellent color retention is provided by
AdvapackTM NEO. Consequently, no color change is expected when mixing standard ratios of
recycled materials (10-20 w%) with fresh PVC dry-blends.
Figures 12, 13, 14: The impact of recycled PVC product produced using AdvapackTM NEO on
rheology is compared against a commercial CaZn product by measuring the fusion time, fusion
torque and equilibrium temperature on a Brabender rheometer.
The ability of the AdvapackTM NEO system not to impact rheology after several processing cycles is
directly linked to the absent, or delayed, cross-linking phenomena with the latent mercaptan
technology. This can be clearly demonstrated by examining the bearing force during the dynamic
thermal stability test on a two roll mill (Figure 15). While the bearing force of the standard lead and
CaZn increase with milling time, the curve stays flat for the AdvapackTM NEO system.

10

NEO 1110 (2.35phr)

9
CaZn one-pack 1 (2.20phr)
Bearing force (kN)

Pb one-pack 1 (2.80phr)
8

5
120 240 360 480 600 720
Milling time (sec)

Figure 15: Bearing force on the two-roll mill

 CONCLUSION

In response to the PVC pipe manufacturers request for high performing, cost effective, lead free
heat stabilizers, Rohm and Haas Company has developed the AdvapackTM NEO system. The
AdvapackTM NEO system relies on “latent mercaptan” technology, which is based on years of
experience in tin mercaptide stabilizer chemistry. The AdvapackTM NEO technology utilizes the high
stabilizing efficiency of mercaptans in a non toxic, odourless, heavy-metal free, organic based
package.
The AdvapackTM NEO systems offer excellent PVC heat stabilizing performance properties and a
wide processing window to achieve good gelation and satisfying melt flow during pipe extrusion
compared to commercial CaZn one-packs.
Due to its delayed cross-linking, consistent color and rheology, AdvapackTM NEO offers enhanced
recycling properties compared to typical CaZn stabilizers.
Sustainability of this innovative lead-free stabilizer for PVC pipes has been assessed using the
SLCA (Sustainability Life Cycle Assessment) tool [12] developed by The Natural Step. Considering
the conclusions of this assessment as well as the technical benefits presented in this article, this
new technology represents an advanced and more sustainable solution for PVC pipes stabilization.

ACKNOWLEDGEMENT

The authors would like to thank BAUSANO & Figli, for their contribution to this work. The authors
also would like to thank the Research and Development, Manufacturing and Technical Service
teams from Spring House (PA, USA), Valbonne (France), and Cincinnati (OH, USA), as well as
Robin Madgwick for the PVC pipe market information.

REFERENCES

[1] [2] A View of the European plastics pipe market in a global scenario, PVC4Pipes, Plastics Pipes
XII Conference, April 2004 M. Raynaud, BP Solvay
[3] Future of PVC piping systems in Europe – a development vector, June 2005, E. Timar, Solvay,
PVC4pipes
[4] PVC stabilizers: a contribution to sustainability, Plastics Additives & Compounding Sept/Oct
2006, p.26-28, Dr G. Wallenwein, Laves Chemie Consulting
[5] [6] Pipe tech Review, TEPPFA, 30 May 2007, ESPA Statistics
[7] A halogenated-containing polymer composition stabilized by a latent mercaptan and a mixture of
zinc carboxylate and zinc chloride, EP1201706 A1, G.K. Norris, Rohm and Haas Company, May
2002.
[8] Latent mercaptans as a heat stabilizer, Patent n° US 6,528,566 B2 - P.B. Adams/ G.K. Norris /
T.C. Duvall, Rohm and Haas Company, March 2003.
[9] Understanding the reactivity of PVC stabilizers with defect sites, K. M. Miller, Rohm and Haas
Company, 2004.
[10] Latent mercaptans as stabilizers for halogen-containing polymer compositions, Publication n°
US 2004/0143044 A1, P.B. Adams/ G.K. Norris / T.C. Duvall, Rohm and Haas Company, July 2004.
[11] PVC recycling doubled, www.plastic-pipes.com, April 2007
[12] A Strategic approach towards sustainability for vinyl additives, PVC 2008 Conference, L.C.
Sederel, M. Hebrard, B. Cora, R. Madgwick, Rohm and Haas Europe Services ApS, April 2008.