Professional Documents
Culture Documents
Outline
1. Introduction Buhler and Micronisers Australasia
Buhler.
Corporate profile.
Buhler is the global specialist and technology partner for plant design & construction and services for the food Industry and production of high-grade functional products. The Groups core technologies are mechanical and thermal processs engineering for producing - foods, - specialty foods, - coating and die cast components. Buhler is the competent partner in consulting, technology, development, project management, and customer service. Annual sales: CHF 1.9 billion Number of employees: 7,700 Active in over 140 countries; Manufacturing sites worldwide: Americas: USA, Brazil Europe: Germany, Switzerland, Spain Africa: South Africa Asia: China, India
Micronisers Australasia.
A small innovative Australian Company
Unique process for the manufacture of nano ZnO for UV protection in personal care and industrial applications Patented additive for the modification and improvement of physical properties of crystalline polymers
TGA/ APVMA facility for the production of active pharmaceutical ingredients and veterinary scheduled products in to fine powders for improved functionality and bioactivity
Main international customers include Buhler Partec, Ciba BASF, Elanco Animal Health Ely Lily, Croda & BYK Chemie
Collaboration with Nanokote Pty Ltd / Nanogate GmbH for nano enhanced coating technologies
Collaboration with Sonic Essentials Pty Ltd for nano enhanced foliar sprays and seed coatings
Issues for Solvent and Water Based Coatings how to become GREEN ?
GOVERNMENT LEGISLATION INDUSTRY TARGETS
SED: Solvent Emission Directive Directive 99/13/EC in force from 31-10-2005 Emission control tightened from 31-10-2007 Directive 2004/42/CE in force from 01-01-2007
NEC: National Emission Ceiling National Emission Ceiling fixed from 2010 NECs tightened up to 2020
CAFE: Clean Air For Europe Clean Air For Europe - thematic strategy due July 2005 EC data (IIASA Report) suggests large reduction beyond SED
World wide regulations have the potential to reduce VOC by about 4 Mt/a *
Water borne coatings are GREEN but they have some limitations
not resistant against moisture not stable against chemical attack not blocking resistant difficult to process hard to dry generally of lower quality than solvent borne alternatives
- A true nano system in any specific application may not relate to primary particle size! - Selection of the correct nano particle or carrier - Stable system - Compatible system - Targeted functionality
Oxylink
What is Oxylink ?
ZnO containing mixture of nano particles in aqueous dispersion Solid content: Density: Viscosity: pH: 40 wt.%* 1.5 g/ml* 4 mPas* 8.5*
TM
UV
O2
O2-
e- electron
OH
3.2 eV hole h+
OH radical
H2O
Past experiments by Micronisers with nano dispersions of ZnO in paints gave no advantage and in some instances negative results
Courtesy of Deakin University ARC Linkage Grant
Ready to use surface modified and stabilized nanodispersions are needed in first place!!!!
Surface modification of nanoparticles ensures compatibility to solvent, formulation and resin
CH
O COOH
CH
OH
CnH2n+1 NH2
Tailored properties by reaction with reactive surface -OH groups hydrophobic / hydrophilic, acidic / alkaline; - potential, polymerizable, etc.
L
L = complexing ligand
De-agglomerated nanoparticles, surface modified and compatible with matrix and processing (tailor-made)
Targeted Functionality - Oxylink nanoparticles lead to increased cross linking in water based coatings ..
Film formation without and with Oxylink nanoparticles*
Application and drying: water evaporates resin droplets stack physical drying (no chemical bonding)
nanoparticles connect reactive groups higher network density results in increased chemical resistance O
H2N
C
O
O C O
* Educated guess. Exact mechanism waits to be explained scientifically. Source: Team working hypothesis.
Resistance against solvents e.g. MEK, IPA MEK double rub resistance IPA double rub resistance Water permeation Blocking resistance
Mechanical properties
- Gloss (60)
Processing parameters
- Drying time
Improved solvent resistance for a range of waterborne resins - Pure dispersion + coalescence agent only
according to ASTM D 5402
250 control MEK double rubs 200 150 100
End point detection: coating destroyed
Oxylink
50
0 Acrylic Styrene acrylic self crosslinking acrylic Acrylic urethane hybrid
Oxylink shows better performance than wax additives: Higher versatility and better humidity resistance
Pure dispersion + coalescence agent only
180 160 MEK double rubs 140 120 100 80 60 40 20 0 Control wax dispersion 1 Oxylink wax dispersion1 + Oxylink
140 120 MEK double rubs 100 80 60 40 20 0 control wax dispersion 1 wax dispersion 2 wax dispersion 3 wax dispersion 4 Oxylink
Slovent resistance: Wax additives work for special formulations only Oxylink good performance in different resins
*1 Rohm & Haas, USA,*2 Evonik Tego Chemie GmbH, Germany, *3 Eastman Chemicals ltd, UK, *4 Bhler PARTEC, Germany *5 Worle-Chemie GmbH, Germany ,*6 Dow Corning, USA
Gloss (60)
60 50
40
30
20
10 0
WG
HBST
OxylinkTM concentration: 0.9 wt.% (solids/solids) End point detection: coating destroyed
OxylinkTM concentration: 0.9 wt.% (solids/solids) End point detection: Starting of gloss decline
MEK
IPA
solvent double rubs 20
MEK
15
IPA
10
40
20 0 WG HBST WG HBST
0 WG HBST WG HBST
TM
50
40
30
20
10
WG
HBST
WOODCOATINGS Oxylink improves blocking resistance: Faster processing and broader application
OxylinkTM concentration: 0.9 wt.% (solids/solids) According to Richtlinie 6, IFT Rosenheim (0 = best; 5 = worst)
5
HBST with Oxylink HBST without Oxylink
TM
4 Blocking rating
WG
With Oxylink
Drying time Gloss (60 ) Gloss retention IPA rub Gloss retention MEK rub Blocking resistance Adhesion (Crosscut, tape) MEK double rub Water permeation Average
80
Blocking resistance
60
40
20
Water permeation
27,3
Gloss (60)
100
without Oxylink with Oxylink
68.4
HBST
With Oxylink
Without Oxylink
Blocking resistance
100 100
41,7 98,8
80
Abrasion resistance
60
40
100
100 100 100 100 100
40,9
20 81,2 100 34,4 82,1
20
Gloss (60)
Water permeation
Water permeation
Average
100
100
94,7
66
without Oxylink
with Oxylink
METAL COATINGS -Two waterborne systems were examined by an independend institute (ILF)
Acronal S 760, (BASF) two coat built up (primer + topcoat) self-crosslinking styrene acrylic latex Fully formulated pigmented coating Neocryl XK-86 (DSM NeoResins+) DTM metal coating Acrylic styrene copolymer emulsion Fully formulated pigmented coating One coat system
METAL COATINGS - following test protocol was applied to steel sheets; grade R 621
Property
Crosslinking and solvent resistance Corrosion protection
Method
MEK and IPA -double rub (ASTM D-5402) Salt spay test according to DIN EN ISO 9227, DIN EN ISO 46282, DIN EN ISO 4628-3, DIN EN ISO 4628-4, and DIN EN ISO 4628-5 Spot test, DIN EN ISO 2812-3 and DIN EN ISO 4628-2; 10 substances* CH for 300 h, DIN EN ISO 6270-2 and DIN EN ISO 4628 1000 h, Type II UV-A bulbs and humidity (DIN EN ISO 11507, process A), evaluation was done using DIN EN ISO 4628 Cross cut method according to, DIN EN ISO 2409 DIN 53150 Reflectivity at 60 and 85 according to DIN EN ISO 2813
Chemical resistance Humidity resistance Weathering resistance Adhesion Drying time Gloss
*: gasoline, water-butyl glycol 90/10, ethyl acetate-butyl acetate 1:1, sodium hydroxide solution (5 %), hydrochloric acid (10 %),
acetic acid (10 %), hand lotion Atrix, aqueous Marlon A 350 solution (50 %), artificial bird excrement and distilled water
METAL COATINGS Acronal Self crosslinking styrene acrylate coating can significantly be improved by Oxylink
MEK double rub
without Oxylink MEK double rub IPA double rub Chemical resistance Adhesion Drying time Gloss Corrosion protection (salt spray test) Weathering resistance Humidity resistance Average 28,3 66,7 92,0 100 100 100 100 80,0 28,7 77,3
with Oxylink 100 100 100 100 100 93,3 100 100 100 99,3
Weathering resistance
100
Humidity resistance
80
60
40
20 0
Chemical resistance
Adhesion
Gloss
Drying time
without Oxylink
with Oxylink
METAL COATINGS -Neocryl Acrylic styrene copolymer DTM coating can significantly be improved by Oxylink
MEK double rub
without Oxylink MEK double rub IPA double rub Chemical resistance Adhesion Drying time Gloss 22,9 60,2 82,3 100 100 100 88,9 71,4 0,0 69,5
with Oxylink 100 100 100 100 100 97,8 100 100 100 99,8
Weathering resistance
Humidity resistance
100 80 60 40 20 0
Chemical resistance
Adhesion
Gloss
Drying time
without Oxylink
with Oxylink
Condensed humidity CH, 300 h; DIN EN ISO 6270-2, DIN EN ISO 4628
PLASTIC COATING - Metallic coating formulation - Starting point formulation for first Oxylink tests
Pigment paste Water Dissolve Disperbyk 192 Stapa Hydrolan IL 161, add while stirring Halox SZP 391 add while mixing Halox 515 add while mixing Diethylene glycol monobutylether add while mixing Let sit over night Homogenize with rotor stator device for 5 min Final coating E-700-Halox Water Ethylene glycolglycol-monobutylether Diethylenglycolglycol monobutylether Dowanol DPM, Dipropylene glycol monomethylether Mix ingredients and adjust pH to 9.0 with 2-Amino-2-Methylpropanol (AMP) Add pH=9 mixture to Neocryl A 662 while stirring Byk 346, add while stirring Drewplus SG-4552, add while stirring Pigment paste, add slowly while stirring 125 0.75 1.25 37.5 15.75 29 7.5 7.5 Ingr./g 59.1 1.5 39.4 1.18 1.18 0.788
0 1 2
No visible change, no sticking Slight sticking, no damage Sticking, stains slightly visible
3
4 5
Drying conditions:
Blocking at 50 C
wt.% Oxylink
PLASTIC COATINGS - Very strong synergy between Oxylink and PTFE wax: No blocking after very short drying time
Drying time 3 hrs instead of 48 hrs 0 = best 5 = worst
2% Oxylink Only
5
3%Oxylink Only 5
0 1 No visible change, no sticking Slight sticking, no damage Sticking, stains slightly visible Blocking, film damaged, no delamination Blocking, slight delamination Full blocking, servere delamination
Wax only
5
5
2 3
1% Oxylink Only
4 5
OXYLINK
Improved Quality of Water based coatings with Oxylink
COST SAVINGS: less expensive resin plus Oxylink vs high cost resin for WG woodcoatings
Drying time (non sticking) IPA double rub resistance
100 80 60 40
Gloss (60)
Without Oxylink: Hybrid coating shows better performance than acrylic coating. Relative performance values: Hybrid coating Acrylic coating
20 0
Scratch resistance
93 71
Performance of acrylic coating can be improved and is significantly better than hybrid coatings by addition of 1 % Oxylink. Relative performance values: Hybrid coating Acrylic coating plus Oxylink
20,0 0,0
67 96
Gloss retention solvent rub, IPA Gloss retention solvent rub, MEK
Abrasion resistance
COST SAVINGS Oxylink provides better performance and lower costs (WG) 9
Price AUD/kg Hybridur 870 (via NRC)# Worleecryl 7461# Resin Cost Difference 8.47 5.94 2.53
8 7
Cost saving 21 %
Worleecryl 7461 plus Oxylink
6
Worleecryl 7461
Oxylink Price
Added cost 1% Oxylink
70.00
0.70
3
2 1
Potential Savings
$ 1.83/ kg
0
Formulation
Hybridur Worleecryl Oxylink 1% solids
Kg of resin
739 762 11
Hybridur 870
COST SAVINGS - Comparison between Hybrid- and Acrylic coating Hybridur 870 vs. Primal AC 337 HBST woodcoating
Drying time (non sticking)
100
Without Oxylink: Hybrid coating shows better performance than acrylic coating. Relative performance values: Hybrid coating Acrylic coating
80 60 40
Gloss (60)
20 0
Scratch resistance
97 76
Gloss retention solvent rub, IPA Gloss retention solvent rub, MEK
Abrasion resistance
100
Performance of acrylic coating can be lifted to the same level as hybrid coatings by addition of 1 % Oxylink. Relative performance values: Hybrid coating Acrylic coating plus Oxylink
80 60 40
Gloss (60)
20 0
Scratch resistance Hybridur 870 Primal AC 337 + Oxylink Gloss retention solvent rub, IPA
87 86
| |
COST SAVINGS Oxylink provides better performance and lower costs (HBST) 9
Price AUD/kg Hybridur 870 (via NRC)# Primal AC 337# Resin Cost Difference 8.47 5.70 2.77
8 7
6
4
Primal AC 337 Hybridur 870
Oxylink Price
Added cost 1% Oxylink
70.00
0.70
3
2 1
Potential Savings
$ 2.03/ kg
0
Formulation
Hybridur Primal AC 337 Oxylink 1% solids
Kg of resin
739 649 8.0
High Quality
Lower Quality
GOOD
POOR
GOOD
POOR
GOOD
POOR
POOR
GOOD
50% improvement in dirt pick up Significantly improved efflorescence control Improved alkali and water resistance Cost saving compared to expensive resin
8 7
Cost saving 6 %
6
5
Low Quality
0.24
Oxylink Price
Added cost 0.2% Oxylink
70.00
0.14
3
2 1
Potential Savings
$ 0.10/ kg
0
Formulation
High quality resin Lower quality resin Oxylink 0.2% solids
Kg of resin
400 400 0.4
1.39
High Quality
Free Oxylink
Performance Parameter
?
Dose Rate of Oxylink
Starting formulations indicate 0.8% to 1.2% dose rate; customer experience ranges from 0.2% to 5.0%
Positive Benefits Identified by Oxylink customer feedback: A lot of properties can be improved consistent with the effects of an extremely efficient crosslinking additive....
Corrosion protection 4% Alkali resistance 4% Dirt pick up 8% Crosslinking 4% UV stability 4% Hardness, Abrasion / scratch resistance 22 %
Chemical resistance 8%
Drying time 17 %
Conclusion
TM
coatings becomes narrower and the hurdles for waterbornes become lower
As a consequence, nanotechnology can play an important role in bringing greener coatings forward