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8/14/2019 Jan 2010 Oxylink Updated Sales Presentation.pdf
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Oxylink Performance
additive.
For better waterborne
Coatings.
Detlef Burgard
Bhler PARTEC GmbH
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Out l ine
1. Introduction Buhler and Micronisers Australasia
2. Issues for Solvent & Water based paints
3. Nanotechnology for waterborne coatings
i. Nano-dispersions
ii. Surface Modification & Functionality
4. OxylinkTM
i. Resin type
ii. Wood
iii. Metaliv. Plastics
v. Cost Savings
vi. Customer feedback
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Buhler .
Corporate profile.
Buhler is the global specialist and technology partner for
plant design & construction and services for the foodIndustry and production of high-grade functional products.
The Groups core technologies are mechanical and thermalprocesss 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
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Micronisers Australas ia.
A small innovative Australian Company
Unique process for the manufactureof nano ZnO for UV protection inpersonal care and industrial applications
Patented additive for the modificationand improvement of physical properties
of crystalline polymers
TGA/ APVMA facility for the production of active pharmaceutical ingredients andveterinary 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 coatingtechnologies
Collaboration with Sonic Essentials Pty Ltd for nano enhanced foliar sprays and seedcoatings
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Issues for Solvent and Water Based Coat ing s how tobecome GREEN ?
Source: SpecialChem - Jun 1, 2009
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 July2005
- EC data (IIASA Report) suggests large reduction
beyond SED
World wide regulations have the potential to reduce
VOC by about 4 Mt/a *
INDUSTRY TARGETS
GOVERNMENT LEGISLATION
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Water bo rne coat ing s are GREEN bu t they have somelimitations
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 lot of these arguments are based on preconception, but there
is also some truth
Thus, there is a continous need to improve the performance ofwaterborne coatings
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Some principals to understand:
- 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
How can Nanotechnology help with these issues ??
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Nanopart ic les and disp ers ions when is i t real???
Oxylink Common In situ agglomerated particle
size of simple nano dispersions
Both systems based on 30 nm ZnO
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What is Oxyl inkTM?
ZnO containing mixture of nano particles in aqueous dispersion
Solid content: 40 wt.%*
Density: 1.5 g/ml*
Viscosity: 4 mPas*
pH: 8.5*
Particle size distribution*
*: typical values, no specifications
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Simple nanodispers ions w ith pure nano ZnO have po tent ial
problems..
OH
h+
e-
H2O
O2
OH radical
UV
3.2 eV
O2-
hole
electronOxideNano
Particle
Generation of reactive oxygen species (ROS) byinteraction of UV with pure zinc oxide particles
can result in interactions with the substrate causing adegradation of the substrate, loss of color & no UV
protection
Past experiments by Micronisers with nanodispersions of ZnO in paints gave no advantage
and in some instances negative resultsCourtesy of Deakin University ARC Linkage Grant
http://images.google.com.au/imgres?imgurl=http://www.isep.org/nus/australi/deakin.gif&imgrefurl=http://www.isep.org/nus/australi/&h=217&w=175&sz=4&tbnid=Hp9w-mzspRQJ:&tbnh=100&tbnw=81&start=1&prev=/images?q=deakin+university&hl=en&lr=&sa=G8/14/2019 Jan 2010 Oxylink Updated Sales Presentation.pdf
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Tailored properties by reaction with reactive surface -OH groups
hydrophobic / hydrophilic, acidic / alkaline; - potential, polymerizable, etc.
Ready to us e surface mod if ied and stabi l ized nanod ispers ions
are needed in f irst place!!! !
Surface modification of nanoparticles ensures
compatibility to solvent, formulation and resin
OH
O
CH CH
OCOOH
NH2
CnH2n+1 L
L = complexing
ligand
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Dispers ions of surface mod if ied nanop art ic les: Produc t ion by
Chemomechanical process ing
Process:
Comminutionand Dispersion
Chemistry:
Surface
Modification
Agglomerated nanoparticles,
Incompatible with matrix and
processing
De-agglomerated nano-
particles, surface modified
and compatible with matrix
and processing (tailor-made)
& = Know-How Package
S
d
Agitator Bead Mill
Process:
Comminutionand Dispersion
Chemistry:
Surface
Modification
Agglomerated nanoparticles,
Incompatible with matrix and
processing
De-agglomerated nano-
particles, surface modified
and compatible with matrix
and processing (tailor-made)
& = Know-How Package
S
d
Agitator Bead Mill
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Targeted Funct ion ali ty - Oxyl ink nanop artic les lead to
increased cross linking in water based coatings ..
Film formation without and with Oxylink nanoparticles*
Stable dispersion: droplets of resin in water
droplets carry reactive groups
Application and drying: water evaporates
resin droplets stack
physical drying
(no chemical bonding)
Coalescence: resin droplets merge
continuous film forms
H2N
O
CH CH2
COOH
Oxylink nanoparticles
are stabilized in
coating formulation
nanoparticles connect
reactive groups
higher network density
results in increased
chemical resistance
C
O
C
O
OO
* Educated guess. Exact mechanism waits to be explained scientifically.
Source: Team working hypothesis.
Oxylink
nanoparticle
resin droplet:
polymer chain
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Increased cro ss l ink ing should lead to bet ter performance
Chemical properties
- Resistance against solvents e.g. MEK, IPA- MEK double rub resistance
- IPA double rub resistance
- Water permeation
- Blocking resistance
Mechanical properties
- Adhesion (Crosscut, tape)
- Abrasion resistance (Taber 100; 200 Cycles)
Optical properties
- Gloss (60)
Processing parameters
- Drying time
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Impro ved so lvent res is tance for a range of waterborne res ins
- Pure dispers ion + coalescence agent only
Significant improvement due to Oxylink
0
50
100
150
200
250
Acrylic Styrene
acrylic
self
crosslinking
acrylic
Acrylic
urethane
hybrid
MEKdo
ublerubs
control
Oxylink
according to ASTM D 5402
End point detection:
coating destroyed
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Oxylink shows better performance than wax additives:Higher versat i l ity and bet ter hum idi ty res is tance
Coatings exposed to
100 % humidityat 40 C
After dryingleft: Wax additiveright: Oxylink
Slovent resistance: Wax additives work for specialformulations only
Oxylink good performance in different resins
Resin base: Worleecryl 7641
0
20
40
60
80
100
120
140
160180
Control wax dispersion 1 Oxylink wax dispersion1
+ Oxylink
MEKdoublerubs Acrylic resin 1
Resin base: Primal AC 337 ER
0
20
40
60
80
100
120
140
control waxdispersion
1
waxdispersion
2
waxdispersion
3
waxdispersion
4
Oxylink
MEKdoublerubs
Acrylic resin 2
Pure dispersion + coalescence agent only
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WOODCOATINGS- Oxy l ink in Ful ly formu lated waterborne
acryl ic
Incredients g
Primal AC-337 ER *1 (45.5%) 655.1
TegoFoamex *2 825 2
Water 100.8
Texanol *3 23.1
Aqueous ammonia (28%) 2.7
Water 201.6
OXYLINK TM *4 6.95
Acrysol RM-12W *1(19%) 6.75
Water 1
EXTERIOR TRANSLUCENT HIGH BUILD STAINBASED ON PRIMAL AC-337 ER (HBST)
*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
Incredients g
Worleecryl 7461*5 762
water 166
Dow Corning Add. 65 02
water:
Ethylen glycol 1:1 42
Acrysol RM 5000 *1 3
Dow Corning Add. 57*6 5
OXYLINK TM*4 11
water 9
EXTERIOR TRANSPARENT WOOD GLAZINGBASED ON WORLEECRYL 7461 (WG)
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WOODCOATINGS - Glo ss (60) remains unchanged
High gloss as a consequence of compatibility between
Oxylink and resin matrix
0
10
20
30
40
50
60
70
80
90
WG HBST
Gloss(60)
with Oxylink
without Oxylink
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WOODCOATINGS Solvent res is tance signi f icant ly imp rovedwi th Oxy l ink
OxylinkTM
concentration: 0.9 wt.% (solids/solids)
End point detection: coating destroyedOxylink
TMconcentration: 0.9 wt.% (solids/solids)
End point detection: Starting of gloss decline
with Oxylink
without Oxylink
0
20
40
60
80
100
120
140
160
WGHBST HBST
Solventdoublerubs
IPAMEK
WG
0
5
10
15
20
25
WG WGHBST HBST
solventdoublerubs
IPAMEK
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WOODCOATINGSOxyl inkTM
accelerates dry ing : Faster
process ing means higher produ ct iv ity
OxylinkTM concentration: 0.9 wt.% (solids/solids)
Time to drying stage 4 (= overworkable) significantly reduced
0
10
20
30
40
50
60
WG HBST
Dryingtime(hrs)
without Oxylink
with Oxylink
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WOODCOATINGS Oxyl inkTM
imp roves block ing res is tance:
Faster processing and b roader app l icat ion
OxylinkTM
concentration: 0.9 wt.% (solids/solids)
According to Richtlinie 6, IFT Rosenheim (0 = best; 5 = worst)
0
1
2
3
4
5
Humidity wood Humidity plastic Temperature wood Temperature plastic
Blockingrating
HBST with Oxylink
HBST without Oxylink
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WOODCOATINGSOveral l properties sig ni f icant ly imp roved
EXTERIOR TRANSPARENT WOOD GLAZING BASED ON WORLEECRYL 7461 (WG)
0
20
40
60
80
100
Drying time (tack free)
Blocking resistance
Water permeation
Adhesion
(Crosscut, tape)
Gloss (60)
Gloss retention
solvent rub, IPA
MEK double rub
resistance
Gloss retention
solvent rub, MEK
without Oxylink with Oxylink
WG With
Oxylink
Without
Oxylink
Drying time 100 58,8
Gloss (60 ) 98,5 100
Gloss retention IPA rub 100 45,5
Gloss retention MEK rub 100 15,4
Blocking resistance 100 100
Adhesion (Crosscut, tape) 100 100
MEK double rub 100 27,3
Water permeation 94,7 100
Average 99.2 68.4
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WOODCOATINGS- Overal l proper ties s ign i f icant ly im proved
EXTERIOR TRANSLUCENT HIGH BUILD STAIN BASED ON PRIMAL AC-337 ER (HBST)
0
20
40
60
80
100
Abrasion resistance
Gloss (60)
Adhesion
(Crosscut, tape)
Water permeationIPA double rub
resistance
MEK double rub
resistance
Gloss retention
solvent rub, IPA
Blocking resistance
without Oxylink with Oxylink
Drying time (tack free)
HBST With
Oxylink
Without
Oxylink
Drying time 100 41,7
Gloss (60 ) 100 98,8
Gloss retention IPA rub 100 40,9
Blocking resistance 100 20
Abrasion resistance 100 81,2
Adhesion (Crosscut, tape) 100 100
MEK double rub 100 34,4
IPA double rub 100 82,1
Water permeation 100 94,7
Average 100 66
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METAL COATINGS -Two w aterbo rne systems were exam ined
by an independend inst i tute (ILF)
Acronal S 760, (BASF) two coat builtup (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
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METAL COATINGS- fo l lowing tes t protocol was appl ied to
steel sheets; grade R 621
Property Method
Crosslinking and solvent
resistance
MEK and IPA -double rub (ASTM D-5402)
Corrosion protection Salt spay test according to DIN EN ISO 9227, DIN EN ISO 4628-
2, DIN EN ISO 4628-3, DIN EN ISO 4628-4, and DIN EN ISO
4628-5
Chemical resistance Spot test, DIN EN ISO 2812-3 and DIN EN ISO 4628-2; 10substances*
Humidity resistance CH for 300 h, DIN EN ISO 6270-2 and DIN EN ISO 4628
Weathering resistance 1000 h, Type II UV-A bulbs and humidity (DIN EN ISO 11507,
process A), evaluation was done using DIN EN ISO 4628
Adhesion Cross cut method according to, DIN EN ISO 2409
Drying time DIN 53150
Gloss Reflectivity at 60 and 85 according to DIN EN ISO 2813
*: 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
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METAL COATINGS -Neocry l Ac ry l ic styrene copolym er DTM
coat ing can signi f icant ly be imp roved by Oxyl ink
0
20
40
60
80
100
MEK double rub
IPA double rub
Chemical
resistance
Adhesion
Drying timeGloss
Corrosion protection
(salt spray test)
Weathering
resistance
Humidity
resistance
without Oxylink with Oxylink
0
20
40
60
80
100
MEK double rub
IPA double rub
Chemical
resistance
Adhesion
Drying timeGloss
Corrosion protection
(salt spray test)
Weathering
resistance
Humidity
resistance
without Oxylink with Oxylink
without
Oxylink
with
Oxylink
MEK double rub 22,9 100
IPA double rub 60,2 100
Chemical resistance 82,3 100
Adhesion 100 100
Drying time 100 100
Gloss 100 97,8
Corrosion protection
(salt spray test) 88,9 100
Weathering
resistance 71,4 100
Humidity resistance 0,0 100
Average 69,5 99,8
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METAL COATINGS - Sign i f icant improvement of hum id ity
resistance
With Oxylink Without Oxylink
Condensed humidity CH, 300 h; DIN EN ISO 6270-2, DIN EN ISO 4628
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PLASTIC COATING - Metal lic coat ing form ulat ion
-Starting point formulation for first Oxylink tests
Pigment paste Ingr./g
Water 59.1Dissolve Disperbyk 192 1.5
Stapa Hydrolan IL 161, add while stirring 39.4
Halox SZP 391 add while mixing 1.18
Halox 515 add while mixing 1.18
Diethylene glycol monobutylether add while mixing 0.788
Let sit over night
Homogenize with rotor stator device for 5 min
Final coating E-700-Halox
Water 15.75
Ethylene glycolglycol-monobutylether 29
Diethylenglycolglycol monobutylether 7.5
Dowanol DPM, Dipropylene glycol monomethylether 7.5Mix ingredients and adjust pH to 9.0 with 2-Amino-2-Methylpropanol (AMP)
Add pH=9 mixture to Neocryl A 662 while stirring 125
Byk 346, add while stirring 0.75
Drewplus SG-4552, add while stirring 1.25
Pigment paste, add slowly while stirring 37.5
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PLASTIC COATINGS - Film appl ication and block ing tes t
Coating applied via doctor blade on Leneta - film, wet thickness 200 m
The coating was dried at room temperature (22 C) for a given time
5 cm x 5 cm samples were prepared
Two respective samples were laid on top of each other (coated sides)
Sample stack is loaded with 2.5 kg for 24 hrs, either at 22 C or at 50 C
Afterwards, the two samples are separated by hand and rated according to the
following scheme:
0 No visible change, no sticking
1 Slight sticking, no damage
2 Sticking, stains slightly visible3 Blocking, film damaged, no delamination
4 Blocking, slight delamination
5 Full blocking, servere delamination
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PLASTIC COATINGS - h igh temperature b lock ing is improved
by Oxylink
0
1
2
3
4
5
0 1 2 3
wt.% Oxylink
Blocking
at50C
Drying conditions:
Temperature: 22 C
Drying time: 48 hrs following the suppliers
recommendations
Blocking test:
Temperature: 50 C Load: 2.5 kg/25 cm
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PLASTIC COATINGS - Very strong synergy between Oxylinkand PTFE wax: No bloc k ing after very sho rt dry ing t ime
0 = best5 = worst
Dried at 22 C & Blocking test was done at 22 C
Drying time 3 hrs instead of 48 hrs
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PLASTIC COATINGS - Samp les after block ing tes t
Control
0 No visible change, no sticking
1 Slight sticking, no damage
2 Sticking, stains slightly visible
3 Blocking, film damaged, nodelamination
4 Blocking, slight delamination
5 Full blocking, servere delamination
Wax only
1% Oxylink Only
3%Oxylink Only
2% Oxylink OnlyOxylink & Wax
Wax Only
0
5
5
5
4
4
5
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OXYLINK
Improved Quality of Water basedcoatings with Oxylink
Cost savings also possible
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COST SAVINGS: less expensive resin plus Oxylink vs highcost res in for WG woodcoat ing s
Without Oxylink:
Hybrid coating shows better performance
than acrylic coating.
Relative performance values:
Hybrid coating 93Acrylic coating 71
Performance of acrylic coating can beimproved and is significantly better thanhybrid coatings by addition of 1 %
Oxylink.
Relative performance values:
Hybrid coating 67
Acrylic coating plus Oxylink 96
0
20
40
60
80
100
Drying time
(non sticking)
Gloss (60)
Scratch
resistance
Gloss retention
solvent rub, IPA
Gloss retention
solvent rub, MEK
Abrasion
resistance
Adhesion
(Crosscut, tape)
MEK double rub
resistance
IPA double rub
resistance
Worleecryl 7461
Hybridur 870
0,0
20,0
40,0
60,0
80,0
100,0Drying time (non sticking)
Gloss (60)
Scratch
resistance
Gloss retention
solvent rub, IPA
Gloss retention
solvent rub, MEKAbrasion
resistance
Adhesion
(Crosscut, tape)
MEK double
rub resistance
IPA double
rub resistance
Worleecryl 7461 + Oxylink
Hybridur 870
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COST SAVINGS Oxyl ink provides better performance andlower costs (WG)
Price AUD/kg
Hybridur 870 (via NRC)# 8.47
Worleecryl 7461# 5.94
Resin Cost Difference 2.53
Oxylink Price 70.00
Added cost 1% Oxylink 0.70
Potential Savings $ 1.83/ kg
0
1
2
3
4
5
6
7
8
9
Worlee
cryl7461
Hyb
ridur870
Worleecryl7
461plusOxylink
# European Prices for resins
Formulation Kg of resin Price AUD per Kg Cost per tonne
Hybridur 739 8.47 $6,259
Worleecryl 762 5.94$5,296
Oxylink 1% solids 11 70
Savings per tonne of paint for resin system $963
Savings per 50 tonne of paint per year $48,150
Cost saving 21 %
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| | |
COST SAVINGS - Comparison between Hybr id - and Acry li c
coat ing Hybr idu r 870 vs. Pr imal AC 337 HBST woodcoat ing
Without Oxylink:
Hybrid coating shows better performance
than acrylic coating.
Relative performance values:
Hybrid coating 97Acrylic coating 76
Performance of acrylic coating can be lifted
to the same level as hybrid coatings by
addition of 1 % Oxylink.
Relative performance values:
Hybrid coating 87Acrylic coating plus Oxylink 86
0
20
40
60
80
100
Drying time (non sticking)
Gloss (60)
Scratch
resistance
Gloss retention
solvent rub, IPA
Gloss retention
solvent rub, MEKAbrasion
resistance
Adhesion
(Crosscut, tape)
MEK double rub
resistance
IPA double rubresistance
Hybridur 870
Primal AC 337
0
20
40
60
80
100
Drying time (non sticking)
Gloss (60)
Scratch
resistance
Gloss retention
solvent rub, IPA
Gloss retention
solvent rub, MEKAbrasion
resistance
Adhesion
(Crosscut, tape)
MEK double rub
resistance
IPA double rub
resistance
Hybridur 870
Primal AC 337 + Oxylink
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COST SAVINGS Oxyl ink provides better performance andlower costs (HBST)
Price AUD/kg
Hybridur 870 (via NRC)# 8.47
Primal AC 337# 5.70
Resin Cost Difference 2.77
Oxylink Price 70.00
Added cost 1% Oxylink 0.70
Potential Savings $ 2.03/ kg
0
1
2
3
4
5
6
7
8
9
Prima
lAC337
Hyb
ridur870
PrimalAC337plusOxylink
# European Prices for resins
Formulation Kg of resin Price AUD per Kg Cost per tonne
Hybridur 739 8.47 $6,259
Primal AC 337 649 5.70$4,259
Oxylink 1% solids 8.0 70
Savings per tonne of paint for resin system $2,000
Savings per 50 tonne of paint per year $100,000
Cost saving 24%
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INTERIOR DECORATIVE CONCRETE SURFACE - Benef it s
Results applicable to Asia for concrete rendered interior surfaces
Cost sensitive segement how to get improved performance at acceptable cost?
However, less expensive resins have lower performance
Use a less expensive resin & Oxylink
50% improvement in dirt pick up
Significantly improved efflorescence control
Improved alkali and water resistance
Cost saving compared to expensive resin
ACRYLIC RESIN EFFLORESCENT ALKALI RESIST WATER RESIST DIRT PICK UP
High Quality GOOD GOOD GOOD POOR
Lower Quality POOR POOR POOR GOOD
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COST SAVINGS Oxyl ink for in ter ior decorat ive conc retesurface
Price AUD/kg
High Quality Resin 50% solids 1.63
Lower Quality Resin 45% solids 1.39
Resin Cost Difference 0.24
Oxylink Price 70.00
Added cost 0.2% Oxylink 0.14
Potential Savings $ 0.10/ kg
0
1
2
3
4
5
6
7
8
9
Low
Quality
Hig
hQuality
LowQualityplusOxylink
#Asian Prices for resins
Formulation Kg of resin Price AUD per Kg Cost per tonne
High quality resin 400 1.63 $652
Lower quality resin 400 1.39$584
Oxylink 0.2% solids 0.4 70
Savings per tonne of paint for resin system $68
Savings per 50 tonne of paint per year $3400
Cost saving 6 %
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Oxylink - fac tors to con s ider to determine dose rate
FreeOxylink
OxylinkCross Linked
PerformanceParameter
Dose Rate of Oxylink
Point of 100% reaction with available
carboxyl groups which will differ withtype and quality of resin
Potential for Oxylink to react with other
substrates and additives especially
when exposed to UV light!
Start ing formu lat ions indicate 0.8% to 1.2% dose rate;
customer experience ranges from 0.2% to 5.0%
?
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Posit ive Benef i ts Ident i f ied by Oxyl ink custom er feedback: A
lot of prop erties can be impro ved con sis tent with the effects
of an extremely eff ic ient c ros sl in king addit ive....
UV stability
4 %
Humidity / water
resistance
8 %
Chemical resistance
8 %
Hardness, Abrasion /
scratch resistance
22 %
Blocking resistance21 %
Dirt pick up8 %
Alkali resistance
4 %
Corrosion protection
4 % Crosslinking
4 %
Drying time
17 %
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Conc lus ion
OxylinkTM
can significantly improve the overall
properties of waterborne coatings
The gap between waterbornes and solvent bornecoatings becomes narrower and the hurdles for
waterbornes become lower
As a consequence, nanotechnology can play an
important role in bringing greener coatings forward
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