Post on 24-Oct-2014
transcript
• Dr. A. Schmid • page 1
Customers’ Seminar
Sofia/BG, May 22nd 2007
Baerlocher Additives for PVC Profiles
Dr. Alexander Schmid
• Dr. A. Schmid • page 2
Overview
PVC stabilisation globally
The situation for Lead stabilisers
Calcium based stabilisers for profiles– Stabiliser development– Stabiliser performance
Conclusion / Outlook
• Dr. A. Schmid • page 3
PVC Profiles: World Market 2006 and Stabilisers
N-America
1400 kt
1400 kt
15%
1200 ktW-Europe
China
Russia
30 kt
India
240 kt
Turkey
Pb
Sn
Ca/Zn
35%
330 kt
CEE
600 kt
5%
• Dr. A. Schmid • page 4
Stabilisers for PVC Pipes & Fittings: World Market
99
%1
%
77
%3
%2
0%
North America
South America
Europe
Africa
Middle EastFar East
Pb
Sn
Ca/Zn
Ca-org.
• Dr. A. Schmid • page 5
Stabilisers for PVC Cables & Wires: World Market
South America
75
%2
5%
North America
Africa
Europe
Middle East
Far East
Pb
Ca/Zn
• Dr. A. Schmid • page 6
S-PVC & Modifier
Co-Polymer
CaCO3
[phr]
TiO2
[phr]
Germany + + 5.0 – 7.0 3.0 (– 6.0)
France + + 5.0 – 6.0 4.0 (– 6.0)
Great Britain + 0 6.0 – 8.0 4.0 (– 6.0)
Turkey + 0 5.0 min. 5.0
Pb stabiliser: 4.5 – 5.5 phrCa-based stabiliser: 3.5 – 4.5 phr
PVC Window Profiles: European Recipes
• Dr. A. Schmid • page 7
PVC Window Profiles: Overseas Recipes
USA China
S-PVC, k-value 68 100 100
CPE 7.0 – 9.0
Acrylate Modifier 6.0
CaCO3 4.0 – 6.0 5.0 – 10.0
TiO2 8.0 – 10.0 5.0
Stabiliser Sn: 2.5 – 3.5 Pb: 4.5 – 5.5
Processing Aid 1.0 0.5 – 1.5
• Dr. A. Schmid • page 8
Situation for PVC Stabilisers – Vinyl 2010
„Voluntary Commitment“ of the European PVC
Industry concerning Lead reduction
(Initiative Vinyl 2010)
Targets for decrease of Lead consumption
(based on year 2000 levels)
• 15% by 2005 • 50% by 2010
• 100% by 2015
• Dr. A. Schmid • page 9
REACH (Registration, Evaluation and Authorisation of Chemicals) to come into force 01.06.2007
Lead based stabilisers expected to be phased out in the EU within 2010 – 2012
Threats expected for certain Tin stabilisers
Baerlocher Calcium based stabilisers are designed to pass REACH process
Situation for PVC Stabilisers – REACH
• Dr. A. Schmid • page 10
Lead versus Calcium based – Cefic Figures
0
10
20
30
40
50
60
70
80
90
100
1999 2000 2001 2002 2003 2004 2005 2006 2007 2008
Co
nsu
mp
tio
n [
%]
Pb Ca/Zn
Forecast
• Dr. A. Schmid • page 11
Stabilisers for PVC Profiles: Forecast
North AmericaEurope
Asia
Pb
Sn
Ca/Zn
• Dr. A. Schmid • page 12
Stabilisers for PVC Pipes & Fittings: Forecast
North America
South America
Europe
Africa
Middle EastFar East
Pb
Sn
Ca/Zn
Ca-org.
• Dr. A. Schmid • page 13
Stabilisers for PVC Cables & Wires: Forecast
South America
North America
Africa
Europe
Middle East
Far East
Pb
Ca/Zn
• Dr. A. Schmid • page 14
Calcium based Stabilisers
Calcium based Stabilisers
… is a common name for all stabilisers without
Pb, Ba, Cd (and Sn)
Available systems:
- Based on Polyols and Metal Soaps
- Based on Hydrotalcite
- Based on Ca/Al-Hydroxy phosphite
- Based on Zeolite
All of these need further co-stabilisers, anti-oxidants and
lubricants in varying amounts
• Dr. A. Schmid • page 15
Evolution of Calcium based Stabilisers for Profiles
Base Stabiliser Dosage Stabilisation
Costs
Base Stabiliser Dosage Stabilisation
Costs
1980s Metal Soaps + 6.0 – 7.0 phr 3× PbPolyols
1980s Metal Soaps + 6.0 – 7.0 phr 3× PbPolyols
1990s Zeolite 5.5 – 6.0 phr 2× Pb
Layered Compounds 4.5 – 5.0 phr
1990s Zeolite 5.5 – 6.0 phr 2× Pb
Layered Compounds 4.5 – 5.0 phr
2000 New Generation 3.5 – 4.5 phr 1.3× Pb2000 New Generation 3.5 – 4.5 phr 1.3× Pb
2005 Latest Generation 3.0 – 4.0 phr similar to
Pb
2005 Latest Generation 3.0 – 4.0 phr similar to
Pb
• Dr. A. Schmid • page 16
Latest Calcium based Stabilisers
General Advantages:
- reduced dosage and costs
- rheology and stabilisation according tocustomer‘s needs
- possible incorporation of processing aid
- potential melt products
• Dr. A. Schmid • page 17
Calcium based Melt Products
Advantages:
Desired, well-known product form
Dust-free
Good flowability, easy dosage
Good handling properties (transport, storage)
Excellent dispersability
Challenges:
Sensitive production procedure
Raw materials limitations
• Dr. A. Schmid • page 18
Physical Properties of Stabiliser Compounds
~1.8
~1.1
0
0,2
0,4
0,6
0,8
1
1,2
1,4
1,6
1,8
[g/c
m3 ]
Pb Ca/Zn
Bu
lk d
ensi
ty
60%
• Dr. A. Schmid • page 19
Specific Gravity of Dryblends
1.47 1.44
0
0,2
0,4
0,6
0,8
1
1,2
1,4
1,6
1,8[g
/cm
3 ]
Pb Ca/Zn
- 2%S
pec
ific
gra
vity
S-PVC 100.00 100.00E-ST 5D 7.00 7.00 phrFiller 10.00 10.00 phrTiO2 3.50 3.50 phrPb (Old Gen) 5.90 / phrCa/Zn (New Gen) / 3.75 phr
• Dr. A. Schmid • page 20
Pb and Ca/Zn Dry Blends
Mixing Curves
0
20
40
60
80
100
120
140
0 20 40 60 80 100 120 140 160
Temparature ºC
Am
ps
Pb Dry Blend Ca/Zn Dry Blend
• Dr. A. Schmid • page 21
Melting characteristics of Pb v Ca Organic tablet stabilisers
• Dr. A. Schmid • page 22
PVC Profile Formulations
White Window Profile Brown Technical Profile
Pb Ca/Zn Pb Ca/Zn Ca/Zn
colour
PVC 100 100 100 100 100
Acrylic Modifier 7.0 7.0 6.9 6.9 6.9
Filler 7.0 7.0 10.0 10.0 10.0
Pigment 3.0 3.0 3.6 3.6 3.6
Stabiliser 5.4 3.8 5.2 3.7 3.1
• Dr. A. Schmid • page 23
Artificial Weathering: XENO-TEST
0
1
2
3
4
5
6
0 500 1000 2000 3000 4000 5000
[Hours]
[b-v
alu
e]
Pb Ca/Zn
White Window Profile
• Dr. A. Schmid • page 24
Natural Weathering: BANDOL (Southern France)
0
1
2
3
4
5
6
7
8
0 6 12 18 24 30 36 42 48 54 60
[Months]
[b-V
alu
e]
Pb Ca/Zn
White Window Profile
• Dr. A. Schmid • page 25
Artificial Weathering: QUV-TEST
Pb
Ca/Zn
Ca/Zn colour
Dark Brown Technical Profile
0 h 1000 h 2000 h
• Dr. A. Schmid • page 26
Pb
Ca/Zn
Ca/Zn colour
0 h 500 h 1000 h
Brown Technical Profile
Artificial Weathering: QUV-TEST
• Dr. A. Schmid • page 27
Technical solutions with Ca-based stabilisers exist
Ca-based stabilisers already price competitive with Pb-based
stabilisers
Baerlocher is engaged to adjust Ca-based stabilisers to REACH
Baerlocher introduces Ca-based stabilisers as melt pastilles
Competent adaptation of coloured Ca/Zn-recipes and pigments
generates an improved weatherability, compared to Pb-
systems
Conclusion - Trends for Calcium based Stabilisers