Highlights on PVC Stabilization for Pipes – Comparison and ... · TEPPFA Forum -2015 Overview PVC...

Highlights on PVC Stabilization for Pipes – Comparison and Trends

13 – 14 April 2015

Dr. Alexander Schmid

TEPPFA Forum -2015TEPPFA Forum -2015

Overview PVC pipes, stabilizers and markets

Worldwide trends for PVC pipes

Comparison of Pb, Ca- and Sn-based stabilizer systems

for PVC pipes

- Performance

- Properties

Summary

Agenda


1.200South America

1.500Europe

1.200Middle East/Africa 1.200

Asia

1.700India

3.800China

Total : 12.900 Ktons

G.R. 2,9%

W Eu G.R. 1%CE Eu G.R. 3,7%

G.R. 6%G.R. 7%

G.R. 5%

Global PVC Consumption 2013Pipes (Ktons)

Source: Baerlocher Estimate/approximations

G.R. 3,3%

2.300 North

America G.R. 5%

Growth has come in the Developing Markets


28.600South America

41.700Europe

33.600Middle East/Africa 32.300

Asia

45.200India

112.500China

Total : 361.800 Tons

G.R. 2,9%W Eu G.R. 1%CE Eu G.R. 3,7%

G.R. 6%

G.R. 7%

G.R. 5%

Global Stabilizer Consumption 2013Pipes (Tons)


G.R. 3,3%

67.900 North

America G.R. 5%

Increasing demand for stabilizers for PVC pipes



Pb stabilisation dominates for PVC pipe systems

North America

South America

Europe

Middle East/Africa

Asia

India

China44

% P

b21

% S

n35

% C

a/Zn

99%

Sn

1% O

ther

s

29%

Pb 6%

Sn

65%

Ca

Bas

ed

86%

Pb

3% S

n11

% C

a/Zn

95%

Pb

2% S

n3%

Ca/

Zn

79%

Pb

2% S

n19

% C

a/Zn

91%

Pb

2% S

n7%

Ca/

Zn


Source: BAERLOCHER ESTIMATE

„Voluntary Commitment“ of the European PVC Industry lead reduction (Initiative Vinyl Plus) by end 2015

Actually ~82% fulfilled

UK: 96%

Germany: 70%

France: 60%

Italy: 67%

Benelux: 82%

Portugal/Spain: 21%

Romania, Hungary, Croatia, Czech, Slovakia Bulgaria: 52%

Turkey: 0%

Austria/Switzerland: 81%

Poland: 69%

Hungary: 100%

Baltic States: 100%Scandinavia: 97%

Ca-based systems arenow the standard in EU


Tin stabilizers Best price/performance ratio for white colored

pipes

FDA regulates material for food contact application NSF/PPI, UL, others: standard and certification for

pipes

Drinking water pipes Max 1 part of Sn per 100parts of resin

California is the leader in material restriction

Rarely tests with Ca-based pipe stabilizer systems

Tin stabilizers still dominate in North America


Pb-based systems dominating in Uruguay, Argentina,Paraguay, Bolivia Clear trend to Ca/Zn

Columbia, Venezuela, Ecuador using Sn

Peru is using Pb, Ca/Zn as well as Sn depending onthe company, but trend goes to Ca/Zn

Brazil: Ca/Zn-based systems already dominate

Trends towards Ca-basedstabilizers in South America


Focus on Pb (small amounts on Sn, Ca-based, noregulation for Pb-free)

China Potable water pipe (Pb-free) (Goal: Pb-freefor U-PVC)

Korea/Australia/New Zealand U-PVC pipe (Pb-free)

Trend setters: China / Australia / New Zealand

Main trend to Ca-based

Pb dominates in Asia(but with some trends to Ca-based)


Generally Pb-based, except forplumbing pipes small trend to Ca/Zn

No regulations for drinking waterapplication Industry prefers Pb (cost-effective)

Ca/Zn used by selected pipeproducers but not promoted due torelative high costs

Pb dominates in India(limited volumes in Ca-based)


Pb-based stabilizer systemsdominating for pipes

Drinking water pipe has to be freeof Pb, As, Cd, Cr(Ministry of Health, Iran)

Sn and Ca-based systems on smallusage level

Slight trend towards Ca-based

Ca-based systems present inNorthern countries of Africa andSouth-Africa

In general Pb stabilizers areused in M. East/Africa


… provide:

Good initial color due to pigmenting properties ofinorganic lead compounds

Good long-term stability

Broad processing window due to long experience ofoperating people

Metal content (Pb): 25 - 35%

Pb-based stabilizers …


linear correlation for Pb-based systems

1,8 phr

2,3 phr

2,8 phr

17

23

27

Dosage HCL [min]

Influence of dosage vsstability


Linear correlation between lead content andthermostability over a wide range

Thermostability can simply be boosted by addition oflead sulfate

Increased lubrication by increased stabilizer dosage

Variation of dosage allows many adjustments

Pb-based stabilizer, properties


… provide:

Initial color sufficient for brown / dark coloredapplications

Thermostability sufficient for standard pipe extrusion orinjection moulding processes

Co-Stabilizers, either organic or inorganic, are applied for purposes such as better initial color, improvedthermostability, light stability, ...

Metal content (Ca, Zn): 1 - 2,5%

Ca-based core stabilizers …


0 min

5 min

10 min

15 min

20 min

25 min

30 min

Congo-Red-Test 20 20 20 min200°C

Mathis-Oven-Test200°C, 5 min

Formulation No. 1 No. 2 No. 3

PVC 100 100 100Filler 7 phr 7 phr 7 phrCa-based Core Stabilizer 2 phr 2 phr 2 phr

Zn-soap ----- 0.2 phr -----

Organic 0.2 phrCo-Stabilizer

Influence ofco-stabilisers


Ca-organic core stabilizer

1,8 phr

2,3 phr

2,8 phr

11

14

16

Dosage HCl [min]



Ca-organic core stabilizer + co-stabilizer

1,8 phr

2,3 phr

2,8 phr

11

16

16

Dosage HCl [min]

Influence of Dosage vsStability


Basic Ca/Zn stabilizer + co-stabilizer

1,8 phr

2,3 phr

2,8 phr

12

13

12

Dosage HCl [min]



Due to use of different Co-Stabilizers more complexsystems

Increase of stabilizer dosage doesn’t always give linearincrease of thermostability

Often improvement of color goes parallel with adecrease in stability

Variation of dosage is more critical

Ca-based stabilizers, properties


… provide:

Formulation concept: Single Components Sn-based component + Calcium Stearate + Lubricants (oxidized waxes, paraffins)

Relative fast fusion behavior of Sn-based formulationscompared to Ca-based formulations Adaption of rheology/stability

Metal content (Sn): 1 - 5% based on overall composition (~17% based on Sn-stabilizer)

Sn-based systems …


Sn-based stabilizer

2,1 phr

2,3 phr

2,7 phr

8

10

17

Dosage HCl [min]



Sn-based stabilisers are typically applied in liquidform

Good initial color

Good long-term stability

Sn-based stabilizers, properties


Stabilizersystem

[phr]HCl

[min]

Pb 2,3 23

Ca-org (darkcolour) 2,3 20

Ca-org (light colour) 2,4 16

Ca/Zn 2,3 13

Sn 2,3 10

0 5 10 15 20 25 30 35 40 45 50 55 60

Comparison of Ca/Pb/Sn-based pipe stabilisers


5 10 15 20 25Stabilizersystem

[phr]HCl

[min]

Pb 2,3 23

Ca-org (darkcolour) 2,3 20

Ca-org (light colour) 2,4 16

Ca/Zn 2,3 13

Sn 2,3 10

Comparison of Ca/Pb/Sn-based pipe stabilisers


Pb-based stabilizers still dominating worldwide

North-America focused on Sn-based stabilizers

Ca-based stabilizers dominating in Europe and South-

AmericaCritical driver: Cost � Solutions to reduce cost:

- High filler level- Multi-layer pipe- More effective use of stabiliser one-packs

Europe is focused on Ca-based stabilisers


… from dark …

… to light colored applications …

static/dynamic thermostability

color holdinitial colorrheology

…

Baerlocher provides tailor-made solutionsfor your pipe application

Highlights on PVC Stabilization for Pipes – Comparison and ... · TEPPFA Forum -2015 Overview PVC...

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