LEAD FREE PIGMENTATION??
Environmentally friendly coloration
Lead Free Pigment
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BU Pigments Coatings 19.11.2013 2 Public, Enviromental friendly coloration BU Pigments, Coatings, 19.11.2013
Contents
1. Global Regulations and Concerns on the Use of Lead containing coatings
2. Lead Pigments – toxicity issue
3. Something about Paint
4. Lead free pigmentation – The available option & alternative 13 Public, Enviromental friendly coloration BU Pigments, Coatings, 19.11.2013 17 Public, Enviromental friendly coloration BU Pigments, Coatings, 19.11.2013
European Chemical Agency (ECHA) Classification and Labelling ◼Classification in Annex VI of Regulation (EC) No 1272/2008 C.I Pigment Yellow 34 C.I Pigment Red 104 EC number: 215-693-7 EC number: 235-759-9 CAS number: 1344-37-2 CAS number: 12656-85-8 Index number: 082-009-00-X Index number: 082-010-00-5 Carc. 1B; H350 Carc. 1B; H350 Repr. 1A; H360Df Repr. 1A; H360Df STOT RE 2; H373 STOT RE 2; H373 Aquatic Acute 1; H400 Aquatic Acute 1; H400 Aquatic Chronic 1; H410 Aquatic Chronic 1; H410
Car. Cat. 2; R45 (may cause cancer) Repr. Cat. 1; R61 (may cause harm to the unborn child) Repr. Cat. 3; R62 (possible risk of impaired fertility) very toxic dangerous for R33 (danger of cumulative effects) the environment N: R50-53 (dangerous for the environment: very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment) Lead Pigments – Toxicity Issues
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Lead chrome –Toxicity Issues
– Lead(II) chromate is a known carcinogen, developmental toxicant, and reproductive toxicant. It is also suspected that lead(II) chromate is a cardiovascular or blood toxicant, immunotoxicant, kidney toxicant, neurotoxicant, respiratory toxicant, and a skin toxicant or sense organ toxicant. (Source from http://en.wikipedia.org/wiki/Lead(II)_chromate) – Although lead poisoning is one of the oldest known work and environmental hazards, the modern understanding of the small amount of lead necessary to cause harm did not come about until the latter half of the 20th century. No safe threshold for lead exposure has been discovered—that is, there is no known amount of lead that is too small to cause the body harm. 23 Public, Enviromental friendly coloration BU Pigments, Coatings, 19.11.2013
Exposure and contact with Lead
– common source of lead exposure for children is lead based paint and the contaminated dust and soil it generates (Clark et al. 1991; Lanphear et al. 1995, 1998; Lanphear and Roghmann 1997; McElvaine et al. 1992; Rabinowitz et al. 1985; Shannon and Graef 1992) – operation of paint mixing, paint spraying (chrome yellow) may be at an average of 1.75 mg/m3 and 3.9 mg/m3 respectively (Elkins, H.B., “The chemistry of Industrial Toxicology” John Willey and Sons, New York and Davis, W.E. & Associates “Emission Study of Industrial Sources of Lead Air Pollutants” Leawood, Kansas 1973) 24 Public, Enviromental friendly coloration BU Pigments, Coatings, 19.11.2013
Some Sources of Lead Exposure 25 Public, Enviromental friendly coloration BU Pigments, Coatings, 19.11.2013
Basic Composition of Paint 26 Public, Enviromental friendly coloration BU Pigments, Coatings, 19.11.2013
Paint Raw Materials – Lead chromate use (intentionally or unintentionally)
Types of Paint Pigment Extender * Dryer
Air drying primer X X X and topcoat Primer, other bases X X types Top coat, other X bases types
*Natural extenders or pigments (like ferro oxides) may contain lead compounds 27 Public, Enviromental friendly coloration BU Pigments, Coatings, 19.11.2013
Typical lead chromate yellow and molybdate orange shades
Lemon Middle Molybdate Public: Environmental friendly colorationChrome Chrome Orange 28 Public, Enviromental friendly coloration BU Pigments, Coatings, 19.11.2013
Lead chromate pigments Advantages and Disadvantages
Advantages (??) Disadvantages
Brilliant & Saturated shades Poor acid and alkali resistance Excellent hiding power Shear sensitive
Excellent flow properties Low colour strength
Relatively low cost Toxicology 29 Public, Enviromental friendly coloration BU Pigments, Coatings, 19.11.2013
Organic pigments Advantages and Disadvantages
Advantages Disadvantages (??) Brilliant & Saturated shades Technical know how Excellent hiding power Excellent flow properties Relatively low cost* No shear sensitive Excellent chemical Resistance Environment Friendly
*Depend on the pigment selection *Lead Free Pigmentation – The Way Forward
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✓ Environmentally friendly ✓ Healthy Manufacturing Environment ✓ Safe disposal to the environment ✓ Potential for improved fastness properties ✓ Branding and Social responsible 32 Public, Enviromental friendly coloration BU Pigments, Coatings, 19.11.2013 *Lead Free Pigmentation Possible and Limitation
– Key issues (Challenges) : • Opacity : requirement - as close to target as possible i.e.. Try to match the contrast ratio • Shade/Gloss : Requirement – Similar shade, minimum metamerism, similar gloss There are no direct drop-in countertypes to lead chromates but there are many alternatives available which are very suitable. It is normal that each shade will need some minor adjustment • Fastness properties : Light / Weather / Solvent / Overpainting Organic pigments offer similar or better fastness properties to lead chrome • Cost of formulation : generally organic pigment alternatives will be at higher cost but by careful pigment selection and formulation the cost differential can be minimized or overcome. 33 Public, Enviromental friendly coloration BU Pigments, Coatings, 19.11.2013
Lead chrome Pigment alternative Challenge - Opacity
– Possibilities : 1. Use of high opacity organic pigments or custom composite pigment 2. Combination with TiO2 (PW 6) 3. Combination with non-toxic inorganic pigments (PY 42, PY 184, PR 101) 4. Light-grey primer to improve opacity (reflectance between 60 – 70%) 34 Public, Enviromental friendly coloration BU Pigments, Coatings, 19.11.2013
Lead chrome Pigment alternative Challenge - Fastness Properties requirements
• Fastness to light and weather (Indoor / outdoor application) • Fastness to solvents & alkali • Anticorrosion property* • Fastness to overpainting • Cost (not price !) • Suitability (environmental friendly) – NEW REQUIREMENT!!
• There are not single pigment could fit for all the requirement, product selection is critical 35 Public, Enviromental friendly coloration BU Pigments, Coatings, 19.11.2013
Lead chrome Pigment alternative Challenge - Anticorrosive
– Chemically active anticorrosive pigments (zinc oxide, zinc phosphate, calcium phosphate and their modification) – Electrochemically active anticorrosive pigments (Zinc and calcium phosphates and their modifications) – Active, cathodic protective anticorrosion pigment (Zinc dust) – Passive anticorrosive pigments (Micaceous iron oxide, aluminium silicates) High Opacity Organic Pigments – 70 Series
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1. High Opacity Organic Pigments Absorption / Reflectance of Light ◼ Organic Yellows and Reds have low absorption, high reflectance ◼ Determined by laws of physics
Scattering of Light ◼ Depends on refractive index difference to binder (= constant for a given paint system) ◼ Depends on particle size of the pigment
➔Find the particle size of organic pigments at which maximum scattering occurs 38 Public, Enviromental friendly coloration BU Pigments, Coatings, 19.11.2013
1. High Opacity Organic Pigments
Light Scattering depends on Particle Size Scattering ability particle size with maximum scattering power
Particle size 39 Public, Enviromental friendly coloration BU Pigments, Coatings, 19.11.2013
1. High Opacity Organic Pigments The "70"-series of pigments Regular PY 83 Opaque PY 83 40 Public, Enviromental friendly coloration BU Pigments, Coatings, 19.11.2013
1. High Opacity Organic Pigments
The "70"-series of pigments – General features compared to standard grades : - Larger particle size / smaller surface area - Higher opacity - Easier to disperse - Better rheology - Increased pigment loading possible - Improved fastness 41 Public, Enviromental friendly coloration BU Pigments, Coatings, 19.11.2013
1. High Opacity Organic Pigments Clariant pigments with optimized particle size
Hostaperm Yellow H4G/H4G 70 Hostaperm Red D3G 70 / D2G 70 Novoperm Yellow 5GD 71 Hostaperm Red E2B 70 Novoperm Yellow F2G Novoperm Red HF3S 70 Novoperm Yellow M2R 70 Novoperm Red F2RK 70 Novoperm Yellow HR 70 Novoperm Red F3RK 70 Hansa Brill. Yellow 2GX 70 Permanent Red FGR 70
Novoperm Orange HL 70 Permanent Orange RL 70
We herewith confirm that substances restricted by directive 2002/95/EC, RoHS (Heavy metals (Cd, Pd, CrVI, Hg), PBB, PBDE) are not intentionally added to all above mentioned products.
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1. High Opacity Organic Pigments * Noted lead chrome pigment is in 20% pigment loading, meanwhile organic pigment is only 10% pigment loading
Relative Opacity - Lead containing and lead free options Lead Free Pigment Opacity
100100 93.9 91.8 9090 87.56 83.7 82.73 80.81 8080 74.1 75.93 69.75 72.18 7070 66.37 6060 50 50 40
40 Contrast Ratio Contrast
Contrast Ratio Contrast 30
P.O.34
P.O.74 P.O.36
30 P.R254 P.Y.74 20 P.Y.83
20 P.Y.151 10 P.Y.184 10 0 0 Lemon Medium Molybdate Host.Y. Host.O.Y. Hansa Nov.Y. HR Nov.O. HL Perm.O. Perm.O. Host. R. Lemon Medium Molybdate Host.Y. H4G Host.O.Y. Hansa Nov.Y. HR Nov.O. HL Perm.O. Perm.O. RL Host. R. Lemonchrome MediumChrome MolydateOrange H4GHost.Y 70. Host.OYBV 01 . Brill.Y.HansaBrill.Y 2GX . Nov.Y70 . Nov.Or70 . 2RLDPerm.O 71 . RLPerm.O 70 . D3GHost.R 70 . chrome Chrome Orange 70 BV 01 Brill.Y. 2GX 70 70 2RLD 71 70 D3G 70 chrome chrome Orange H4G 70 BV 01 2GX70 70 HR 70 HL 70 2RLD 71 RL 70 D3G 70 70 43 Public, Enviromental friendly coloration BU Pigments, Coatings, 19.11.2013
Color Range for Lead Free Pigmentation
100
95 Hansa Brilliant Yellow 2GX 70
Medium Chrome Host. Yellow H4G 70 90 Lemon Chrome
85 Nov. Yellow HR 70 Host. Oxide Yellow BV 01 80
Permanent Orange 2RLD 71 75
Permanent Orange RL 70 Chroma (c) 70 Molybdate Orange
Nov. Orange HL 70 65 Host. Red D3G 70
60
55 25 35 45 55 65 75 85 95 105 Hue (h) 44 Public, Enviromental friendly coloration BU Pigments, Coatings, 19.11.2013
2. Optimizing the use of opaque inorganic pigments Combine with:
TiO2 (P.W.6) Iron Oxides (P.Y.42, P.R.101) Nickel / Chrome Titanates (P.Y.53. P.Br.24)
✓ Refractive Index Inorganic Pigment Refractive Index Calcium carbonate 1.55 Barium sulfate 1.64 Zinc oxide 2.02 Titanium dioxide (Rutile) 2.76
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2. Optimizing the use of opaque inorganic pigments 46 Public, Enviromental friendly coloration BU Pigments, Coatings, 19.11.2013
2. Optimizing the use of opaque inorganic pigments 47 Public, Enviromental friendly coloration BU Pigments, Coatings, 19.11.2013
2. Optimizing the use of opaque inorganic pigments Inorganic Pigments Contrast Ratio Value (at 20% conc.) Full Shade
Lemon Chrome Yellow 74.10
Middle Chrome Yellow 83.70
Molybdate Orange 93.90
Organic Pigments / Contrast Ratio Value Organic Pigments combination (1:1) (at 8.0% conc.) Full Shade 4:1 TiO2 1:1 TiO2
Hostaperm Yellow H4G 63.51 80.16 90.11
Hansa Brilliant Yellow 2GX 70 72.18 80.03 86.89
Novoperm Yellow HR 70 74.44 82.34 90.24
Novoperm Orange H5G 70 72.41 87.07 93.75
Permanent Orange RL 70 91.80 94.41 95.96
Novoperm Orange HL 70 82.73 92.11 96.37
Hostaperm Red D3G 70 87.56 92.96 96.88 48 Public, Enviromental friendly coloration BU Pigments, Coatings, 19.11.2013
3. Light-grey primer to improve opacity & different film thickness Use light grey or beige primer with a reflectance between 60 – 70% (not white or black)
Relative opacity of different pigment types Standard organic yellows > 250 m Opaque organic yellows ~120- 50 m Lead chrome yellows ~60-80 m
Standard organic orange/reds > 150 m Opaque organic orange/reds ~ 70-80 m Molybdate orange ~ 35-50 m (Dry Film Thickness)
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Opacity effect of undercoat shade
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Opacity effect of undercoat shade
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Opacity and Price RAL 1012 Lemon Yellow
Lead free Lead free Lead containing High performance Economic Arrovide Yellwo G Hansa Brilliant Yellow 26.2% 26.23% 63.69% PY34 151 2GX 70 Hostaperm Green 0.1% 10.34% PY42 5.74% PY42 GNX
33.4% PBR24 63.35% TIO2 30.5% TIO2
7% PY42 0.08% PBK7 0.06% PBK7
33.3% TIO2
Pigment calculated 26.9% 23.6% 38.9% on solid binder
Pigment in wet paint 11.8% 10.1% 16.7%
54m Opacity 53m 55m
USD/KG/Loading 1.16 0.53 0.70 approx. Public BU Pigments, Coatings, 19.11.2013
Opacity and price RAL 3000 Flame Red
Lead free Lead free High performance Lead containing Economic
46.68% Novoperm Orange HL 70 4.7% Hansa Brilliant Yellow 2GX 70 89.68% PR104
22.19% Hostaperm Red D3G 70 56.8% Permanent Red F3RK 70 3.71% Arrovide Violet 201
11.56% PR101 23.4% PY42 0.09% PBK7
17.57% TiO2 6.2% PR101 6.52% TiO2
8.9% TiO2
Pigment calculated on 11.5% 11.2% 23.9% solid binder
Pigment in wet paint 5.4% 5.0% 11.0%
52m Opacity 59m 56m
USD/KG/Loading 0.99 0.63 0.69 approx. 53 Confidential, Lead free BU Pigments, Coatings, 19.11.2013
Price calculation by different pigment
Formulation Formulation Formulation Formulation Unit 1 2 3 4 Price/USD PY151 52 45 28 29 22.40
PY139 25 21 16 35.00 PY110 19 56.00 PY42 23 14 16 12 2.40 PBR24 20 8.00 PY53 40 40 9.60
Price USD/KG 20.95 19.37 16.10 21.26
5% pigm. Loading 1.05 0.97 0.81 1.06
10% pigm. Loading 2.10 1.94 1.61 2.13 54 Public, Enviromental friendly coloration BU Pigments, Coatings, 19.11.2013
RAL Shade formulations
– Approach : Match RAL shades, popular shades by combining non-toxic pigments.
Pigmentation Recommendations for Powder Coating Formulations for RAL, the Paint Industry Corporate and other Shades
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Summary
– No direct drop-in replacements for lead chromate pigments BUT …. – Environmentally friendly alternatives are available – Wide range of fastness properties and costs can be selected according to specific application needs – Similar opacity levels can be achieved Main advantage for replacement : Sustainable products that are environmentally safe End of the Presentation Thank you
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BU Pigments Coatings 19.11.2013