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WWW.SLF.CC NR 3 OKTOBER 2013 58. ÅRGÅNG
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NR 1 MARTS 2007 53. ÅRGÅNG
WWW.SLF.CC NR 3 OKTOBER 2013 58. ÅRGÅNG
Web GuideRaw materials Decorative coatings Additives/fillers/pigments
Fillers/Chemicals Colorants/tinting equipments
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Pigments
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www.cibasc.com
www.landora.se
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Additives/Pigments
Industrial coatings
Decorative coatings
www.huntsman.com/pigments
Web GuideRaw materials Decorative coatings Additives/fillers/pigments
Fillers/Chemicals Colorants/tinting equipments
Decorative coatings Raw materials
Pigments
www.termidor.sewww.bayermaterialscience.com www.beckers.se
www.cpscolor.com
Additives/binders/pigments
www.cdm.se
www.alsiano.comwww.alcro.se
www.cibasc.com
www.landora.se
www.beckers-bic.com
Additives/Pigments
Industrial coatings
Decorative coatings
www.huntsman.com/pigments
Web GuideRaw materials Decorative coatings Additives/fillers/pigments
Fillers/Chemicals Colorants/tinting equipments
Decorative coatings Raw materials
Pigments
www.termidor.sewww.bayermaterialscience.com www.beckers.se
www.cpscolor.com
Additives/binders/pigments
www.cdm.se
www.alsiano.comwww.alcro.se
www.cibasc.com
www.landora.se
www.beckers-bic.com
Additives/Pigments
Industrial coatings
Decorative coatings
www.huntsman.com/pigments
www.ncscoloursystem.com
www.brenntag-nordic.com
www.r2group.eu
Ready foryour company
www.acmgroup.se
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www.phoenix-paint.dk Your Manufacturing PartnerCoatings & Resins
www.southcoat.com
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SK
ANDINAVISKA
LA
CK
TEKNIKERS FöRB
UN
D
Few words from the President
I trust everyone has had a relax-ing summer and enjoyed the fine weather all over Northern Europe. Most people I have met after the holiday period have said that it has been a fantastic summer, and I likewise hope it has been for you. I myself have enjoyed my daily walks along the coast in Halmstad where the sun is always shining all year round!When you receive this issue most of you will be back to the daily working life and doing your best to strengthen the Nordic economy. The SLF is also busy revamping our webpage. This work is being lead by Anette Nordskog, chairperson for Norway’s NMLF. We are using the services of the Norwegian Promo-tion Group (NPG) to completely re-design the SLF webpage. The NMP was behind the SLF congress pages used for the Norwegian and Finnish SLF congresses and we are happy to continue our work togeth-er with them. The web address will change from slf.cc to a new address which we hope we can inform you about in the next issue. The existing national web pages will be linked into the new SLF home page.The organising committee for the next SLF congress has started its work preparing the congress. This is SLF’s major activity and requires significant input from myself and the organising committee. The other committee members consist of Tony Reinler, Ann-Karin Gun-narsson, Carina Stjernman,Martin
Lamkén, Peter Feher and Peter Weissenborn. This team has started well and I am already proud to an-nounce that the next SLF congress will be held in Sweden on 16-18 September 2015 at the Post Clarion Hotel in central Gothenburg. Please book in this date in your calendar. I will keep you posted with import dates for paper submissions and reg-istration. If any SLF member would like to help, have any ideas or sug-gestions for the congress then please contact me.I am also working more closely with Simon Greve, our editor of Färg och Lack Scandinavia, with the aim to improve the content of the jour-nal and ensure punctual delivery. This is the third of four issues for 2013, and you should receive issue no. 4 before Christmas.In October we plan to transfer our current CSI secretariat to another CSI organisation. I will be travel-ling together with Simon Greve (CSI Secretary) to the annual CSI meeting in Japan on 23-26 Octo-ber. There will be much discussion about the future roll of CSI and its benefits for members. SLF will sup-port a proposal from Australia for a more simple form of membership without the need of expensive an-nual meetings.If any member would like to dis-cuss any SLF matter with me please feel free to send me an email at [email protected] or telephone +46735936301.With this issue I wish you a warm and colourful autumn and encour-age all members to participate in the coming local events in Denmark, Sweden, Norway and Finland. Your support by attending local meetings is very important for the continued success of your national organisa-tions and the SLF. Please also feel free to contribute with text and photos to our journal, by sending material to Simon Greve.
Best regards,Laszlo Guitman, SLF President15 September 2013
ISSN 0106-7559
MEDLEMSBLAD FÖR SKANDINAVISKALACKTEKNIKERS FÖRBUND – SLF
INNEHÅLL SidFew words from the president 3Novel Hydroxyethylcellulose (HEC) for Direct Dry-Powder Addition 4Emballator Ulricehamns Bleck 10Epoxy coatings Based on Nanotechnology 12Industrinyt 21
PRESIDENTLaszlo GuitmanBäckagårdsvägen 50SE-302 74 Halmstad Telefon: +46735936301Mail: [email protected]
GENERALSEKRETÆR/ANSVARLIG UDGIVERPeter WeissenbornSherwin-Williams Sweden ABP.O.Box 2016SE-19502 Mä[email protected]+46 381 262 60
CHEFREDAKTØRSimon GrevePhoenix PaintDK - 5900 RudkøbingTelefon +45 6251 2828Fax +45 6251 2727Mobile +45 3167 7958Mail: [email protected]
ANNONCER:Simon Greve
OMSLAGSBILD:Trykkeriet.net
4
Novel Hydroxyethylcellulose (HEC) for Direct Dry-Powder Addition
Prachur Bhargava, Abe Vaynberg, Dehua Liu, Paul Gillette
Ashland Inc., Ashland Specialty Ingredients, Wilmington DE
Introduction
Hydroxyethylcellulose (HEC) has been the leading thickener for waterborne architectural coatings for more than 50 years. It is widely used as the primary rheology modifier in waterborne latex paints globally. HEC provides unique features and advantages to latex-based paints. HEC is used in a broad range of formulations to ensure the delivery of properties such as full-bodied rich consistency, freeze-thaw stability, excellent sag resistance, dillution tolerance, excellent compatibility with surfactants and colorants, and pH and electrolyte stability. Today, the majority of HEC is sold as a powder. The powder form of HEC offers convenience in product shipping (no presence of water or additional solvents) as well as storage. HEC is also available in a modified form, improving paint performance with enhanced spatter resistance and leveling properties through an associative mechanism. As with any water-soluble polymer powder, HEC is susceptible to lump formation when added dry in water-based systems. HEC is also available in a treated form which mitigates lumping under certain conditions and enables utilizing HEC by specific methods. These methods of utilization are given in Figure 1a.
Utilizing HEC in the Let-Down stage of the paint-making process requires preparing a slurry or solution in water beforehand. Preparing a solution requires extra water, as only a 1-3 wt.% solution will remain pumpable. Additionally mixing and storage issues can also be encountered. A 10-15% wt. % slurry is also prepared in some instances - a skill and labor intensive extra step. It requires high discipline in operations to avoid a host of issues, such as gelling of the slurry in the pipes. There is significant sensitivity of the stability of the slurry to pH and temperature. It also requires a fixed set-up. The only stage where HEC powder can be added dry, avoiding any lumping, is at the beginning of the grind stage. The grind stage is a high-shear operation; mixing at very high speed can disperse HEC particles and prevent lumping in most cases. However, this approach, which is utilized by number of paint manufactures, has several inherent disadvantages. High viscosity of the mix in the grind phase can cause excessive power consumption, poor mixing, potential motor overload, excessive heating of the batch causing degradation of organic components and long cycle times when transferring the grind phase to the Let-Down tank in the case of a two-stage paint manufacturing process. This high shear operation can also cause degradation of the HEC which can cause inconsistent batches.
A novel Hydroxyethylcellulose (HEC) was developed for direct dry powder addition. The direct-add HEC can be added in the paint making process as a dry powder. It has been designed in such a way that no changes in the rheology profile and paint properties will be observed and the performance attributes of HEC technology are maintained. Providing unprecedented flexibility to the paint manufacturer, the direct-add HEC can be added to the Let-Down stage under lower shear mixing as well as at the end of the grind stage. Figure 1b depicts new opportunities for paint manufacturers with the novel direct-add HEC.
Origin of Lumping and ‘Lump Free’ Performance of Direct-Add HEC
Figure 1 (A) Utilization of conventional HEC (B) Utilization of Novel direct add HEC
B A
55
Figure 4 Direct add HEC performance in (A) Vinyl Acrylic Paint 70PVC (B) Styrene acrylic paint 83PVC 83 PVCHEC
Water-soluble powder lumping results from polymer particles beginning to dissolve while still in close proximity of each other. Such agglomerates or lumps can be persistent and take days to dissolve. If the timescale for the particles to initiate dissolution and stick is shorter than the timescale for their dispersion, lumps are formed as shown in Figure 2 at the bottom. On the another hand, if the timescale of particles to initiate dissolution and stick is longer than the timescale for dispersion, particles can be dispersed prior to beginning of dissolution and lumps can be avoided as shown in Figure 2 at the top.
Lump Free Performance of Direct Add HEC
The dissolution of HEC was monitored by following viscosity build up with time upon HEC addition. Novel direct-add HEC was added as a dry powder and compared to slurry addition of conventional HEC and dry addition of conventional HEC. Figures 4a and 4b illustrate the performance of direct-add HEC product in two different paint formulations: vinyl acrylic/70 PVC and styrene acrylic/83 PVC. The dissolution profile obtained with the direct-add HEC product (red line) when added dry is similar to the dissolution profile of the conventional HEC added as a slurry(blue line). Unlike the extensive lumping resulting from direct dry addition of the conventional HEC, the direct-add HEC product did not have any lumps.
A B
Figure 2 Water soluble powder lumping and dispersion
6
Figure 5 Direct add HEC performance vs. a conventional HEC on 2,000 gram scale (A) Paint surface prior to addition of conventional HEC (B) Paint surface 30 minutes after addition of conventional HEC (C) Paint surface prior to addition of direct add HEC (D) Paint surface 30 minutes after addition of direct add (E) HEC lumps recovered in the case of conventional HEC direct addition experiment.
An example of the larger-scale performance of the direct-add HEC product will be discussed next. Figure 5 shows photographs of the surface of 70PVC vinyl acrylic paint in beaker at 2,000 gram scale before HEC addition and 30 minutes after the addition. The conventional HEC formed persistent lumps (top pair of images) and failed to provide desired viscosity to the paint formulation with the final KU viscosity measuring 76 KU. In contrast, the direct-add HEC dissolved lump free (bottom pair of images), bringing the paint viscosity to the desired 98 KU. The photograph (top right) depicts lumped HEC recovered from the experiment carried out with the conventional HEC.
In all the above experiments, the paints made by adding conventional HEC as slurry and direct-add HEC as a dry powder were subjected to extensive storage stability and application tests and the paint properties were identical. Thus direct add HEC provides the functionality to be added dry to the paint while still maintaining the rheology profile and application properties provided to paint by conventional HEC.
Benefits of Direct Add HEC
For customers who currently use a significant portion of the HEC in the grind stage, moving the HEC addition partly or completely to the Let-Down stage by using direct add HEC can provide significant benefits. Using less HEC in the grind results in a lower viscosity grind. Viscosity across both low and high shear rates is several orders of magnitude lower when only 10% HEC is added in the grind. The viscosity profiles were used to generate a simulation to understand mixing under both the above conditions. The simulation output shows the mixing speed in m/s throughout the tank geometry which is shown in Figure 7. It is clear that the mixing is much better with 10% HEC in the grind versus 100% HEC in the grind.
A B
C D
77
In both the above cases the simulation was also used to estimate power draw during the grind process. The results are shown in Table 1 below. As is evident in the far right column, the simulated power draw reduced five times when adding only 10% HEC in the grind when compared when adding 100% HEC in the grind. Moreover, the viscosity and volume averaged velocity indicates lower viscosity and better mixing speeds for case of 10% HEC in the grind.
Grind Scenario Apparent Viscosity
(cps)
Volume Averaged Velocity
(m/s)
Volume Averaged
Shear (1/s)
Total Power Draw (KW)
10% HEC in the grind 1027 0.16 2.94 1.88
100% HEC in the grind 85505 0.06 1.71 10.54
The lower viscosity of the grind also reduces cycle time in case of two tank operations where the grind is pumped from the grind vessel to the Let-Down vessel. Lower viscosity results in faster pumping speed and less wear and tear of the pumps. The lower grind viscosity also helps to reduce motor overload and wear and tear of the motor.
For processes where conventional HEC is added as a slurry or solution in the Let-Down stage, direct-add HEC can be added as a dry powder to the Let-Down stage. This will result in cycle time savings as it will eliminate the slurry or solution preparation step and also save slurry or solution pumping time. Issues related to HEC solution storage are also avoided. Further issues like clogging of lines due to fast swelling of HEC slurries will be eliminated. In addition, adding the HEC as a dry powder frees up water which can be used to make pigment slurries or high solids paint. The extra water can provide the additional flexibility to the manufacturing. Next we review two specific cases where some of the above mentioned benefits were quantified in paint production trials.
A B
Table 1 Mixing and power draw simulation results for 10% of HEC in the grind versus 100% HEC in the grind
83 PVCHEC
Figure 7 Mixing simulations for grind operation (A) 10% of HEC in the grind (B) 100% HEC in the grind
83 PVCHEC
8
Case Study 1: Power Savings from Direct Add HEC
Paint making process was a single tank process at 1MT scale. The paint being manufactured was a 70PVC styrene acrylic based paint. Utilizing conventional HEC 70% of HEC was added in the grind and 30% in Let-Down. The HEC in the Let-Down was added as a 3wt.% % solution and thus limiting the amount of HEC which can be added in the Let-Down stage. HASE was also added in Let-Down stage. Utilizing direct add HEC only 30% of HEC was added in the grind stage and 70% added in the Let-Down stage as a dry powder and no HASE was added. Final Stormer Viscosity of the control paint was 100 KU while that using Novel HEC was 103KU. Current (AMPS) measurements were taken during grind stage of the paint in both the above cases. The voltage, current and power calculation are shown in table 2 below
Control
Direct Add HEC
60 60 minutes grind processing
380 380 VAC 22.5 17.5 Amps 8.55 6.65 KW-hr
Savings per batch were calculated as 8.55-6.65=1.99 KWH or 30% of grind processing energy cost. Other benefits observed were consolidation of thickeners, elimination of HASE, lower work load for operators, avoid preparing, storing and feeding 3% solution of HEC and free up water.
Case Study II: Cycle Time Reduction
The paint making process in this case study was a two tank process with a 8MT scale Let-Down tank. The paint being manufactured was a 78 PVC styrene acrylic based paint, utilizing conventional HEC. 70% of HEC was added in the grind and 30% in the Let-Down stage. Once the grind is made, it is pumped to the Let-Down tank, then 2wt. % solution of remaining HEC is added and mixed for 60 minutes. Utilizing direct-add HEC, 30% HEC was added in the grind and 70% in the Let-Down stage. For the most optimal process, novel direct-add HEC was added as a dry powder to the Let-Down stage as the mill base was being pumped to the Let-Dow tank. In this case, the lower grind viscosity resulted in better mixing, thus shorter grind time. The grind was pumped faster and it was evident that the load on the pump motor was reduced. The Let-Down time was reduced as HEC dissolution initiated earlier in the Let-Down process while the grind was being pumped. Table 3 shows the tabulated data.
Run Conditions Grind (min)
Grind Pump Time
Let Down (min)
Total (min)
Time Savings
(min)
Time Savings
(%) Conventional HEC
50% HEC added to grind, balance (50%) added as solution to Let-Down
60 35 50 145
Table 2 Power consumption data and calculation from trial
83 PVCHEC
99
The cycle time was reduced by 23%, which can benefit the paint manufacturer by providing ability to produce more batches a day and/or avoid overtime. Other benefits which were observed were reduction in wear and tear of pumps, avoiding HEC solution preparation and pumping/feeding step and free up water. In both the above plant scale trials the paints made with direct-add HEC provided equivalent application performance as the paints made with conventional HEC. Paints were subjected to long term stability with positive results in all cases.
Conclusion
A novel HEC for direct dry-powder addition has been developed. The direct-add HEC can be added as a dry powder to any point in the paint making process providing unprecedented flexibility to the paint manufacturer. This will result in significant benefits including cycle time reduction, lower grind viscosity, energy savings, free up water, avoidance of issues with slurry and solution preparation and storage and others. The rheology and paint application properties provided by direct add HEC are identical to those provided by conventional HEC. Paint production trials utilizing direct add HEC have substantiated a number of benefits as was elucidated by case studies presented in this paper. The direct-add HEC has been designed to offer excellent dispersion and rapid dissolution under a broad range of process conditions providing wider applicability of HEC and a more robust performance when compared to conventional treated HEC.
Direct add HEC
30% HEC added to the grind, balance 70% as dry powder in the Let-Down during transfer of grind
55 21 35 111 34 23%
10
Emballator Ulricehamns Bleck grundades 1907 och redan från starten var metall, s.k. bleckplåt, det givna materialet. Företaget som ägs av Herenco koncernen i Jönköping (pri-vatägt sedan 4 generationer) och började tillverka sin första färgburk på 50-talet. Med en överlägsen marknadsposition på den nordiska färgmarknaden har man sedan ett antal år skördat framgångar ute i Europa. Även om marknaderna skiljer sig åt efterfrågas innovation, kvalitet och lever-anspålitlighet över praktiskt tagit hela värden. Företagit har 3 produktionsenheter, förutom Ulricehamn även i Nybro och Bradford, England. Totalt omsätter dessa 3 bolag ca 850 miljoner sek och har 300 anställda.
Ulricehamns BleckNågra mil öster om Borås ligger den inom Emballator
Metal Group största anläggningen, Ulricehamns Bleck. Här sker största delen av produktutvecklingen och fab-riken har sedan många år tillbaka gjort stora investeringar i moderna maskiner och robotar. Detta har gjort anläggnin-gen till en av Europas modernaste inom sin bransch tack vare kontinuerliga investeringar, hög teknisk kompetens, ständigt pågående LEAN-arbete och en dedikerad person-al. Årligen produceras över 30 miljoner burkar men man har kapacitet för mer.
ProduktutvecklingProduktutvecklingsavdelningen i Ulricehamn arbetar konstant med att finna nya innovationer och tekniska lösningar. Det klassiska problemet med att öppna och åter-försluta en plåtburk stör högt på agendan. Färginnehållet
EmballatorUlricehamns Bleck
Nordens ledande metallemballage tillverkare med sikte på övriga världen
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K U R S E N G E R D I G E N G R U N D L I G G E N O M G Å N G A V S A M T L I G A F Ä R G S Y S T E M
Diplomkurs Färger och Lacker
Grundkurs i färg- och lackkemi med kunskapskontroll och DiplomeringKursen hålls vid åtta tillfällen i centrala Stockholm. Medlemmar i SLF erhåller 10% kursrabatt.www.stf.se
Kontakt för anmälan och information:Karin Stening, 08-586 386 22, [email protected] Kursstart
5 nov
S T F I N G E N J Ö R SU T B I L D N I N G
Din partner för kompetensutveckling
måste skyddas, behålla dess kvalitet och samtidigt förmedla ett budskap eller framhålla ett varumärke, vilket innebär att burken skall vara oerhört tät men samtidigt enkel att öppna och återförsluta. En inte helt enkel kombination. I takt med fortsatt produktutveckling av färgsystemen och därmed övergång till vattenbaserade produkter minskar även behovet av metallemballage och viss övergång till plastemballage har förekommit. Detta till trots gör att Ulricehamns Bleck ser positivt på framtiden och genom att erbjuda hög kvalitet, nya innovationer och en ”rätt produkt till rätt pris” finns fortfarande stora marknadsand-elar att erövra.
Hybrider, här för att stanna?På senare år har bolaget utnyttjat kompetensen från övriga bolag inom koncernen, t.ex. Emballator Lagan Plast i Ljungby. Här har man genom gemensam produktutveck-ling skapat s.k. hybridprodukter där man kombinerar plåt och plast. Genom att använda plasten som öppnings och låsningsmaterial i locket har man bibehållit plåtens styrkor och samtidigt utnyttjat plastens flexibilitet och lätthanterlighet. Första produkten lanserades 2006 och i dagsläget tillverkar man ett 10-tal hybridprodukter. Även om produkten nått stora framgångar, både nationell och internationellt, finns knappt några konkurrenter inom detta område vilket bevisar att kombinationen av två mate-rial är en komplex och svårhanterligt kombination vilket
kräver stor kompetens inom bägge materialområdena.
Framtidens färgburkOm vi kikar in i framtiden, vilka sorters emballage kom-mer att efterfrågas? Helt klart är att öppningsförmågan och dess hantering är i fokus. Vidare kommer miljöaspek-ter kring materialet och vilka resurser som krävs vara av intresse. Kanske kommer vi se fler materialkombinationer och fler innovationer såsom integrerade verktyg, trans-parenta ytor för att synligöra innehållets kulör, smartare handtags lösning, rektangulär, oval eller rund form? Med en konstant dialog med färgbranschen hoppas Emballator vara det självklara förstahandsvalet även de kommande 106 åren.
Henric WiklundCommercial DirectorEmballator Metal Group
12
EPOXY COATINGS BASED ON NANOTECHNOLOGYBY USING
ORGANIC INORGANIC HYBRID POLYMERS
Monika Pilz, Tina Helland*, Christian R. Simon, Juan Yang, Ferdinand Männle, Huaitian Bu, Olav Marstokk*
SINTEF Materials and Chemistry, Forskningsveien 1, N-0373 Oslo, Norway * Jotun A/S, Rosenvoldsgate 19, N-3211 Sandefjord, Norway
ABSTRACT
Polymer materials are utilized in an increasing number of product applications, such as components and coatings in the field of automotive, aeronautics and marine applications. The application of polymer materials in new categories of products is often limited by their properties but also by new environmental regulations coming up in the EU within the recent years. It is therefore a continuous demand for development of polymer products with improved properties e. g. with respect to increased scratch resistance, improved weather resistance, increased UV resistance, increased chemical resistance and improved properties with respect to antioxidation, anticorrosion etc. and at the same time to meet the legislative requirements. In addition to pure polymers, there has also been developed new products based on so-called hybrid organic inorganic materials that combine advantages of inorganics and polymers which open the possibility for tuning surface and matrix properties of polymers. Organic/inorganic hybrid polymers (HP) having properties similar to hyperbranched polymers have been prepared in our laboratory. These may be applied e.g. as additives for polymer products like thermoset plastics and in lacquers and other types of coatings for surface protection. Used in appropriate amounts and with convenient particle size, such hybrid polymers may significantly improve the properties of paint formulations like wear resistance/scratch resistance and/or weather resistance. It is shown in this paper that epoxy formulations for (top coat) industrial applications modified by reactive HP additives showed improved mechanical properties and UV resistance of various test species with respect to unmodified references. Thus, epoxy formulations are showing various material properties which are comparable to those of polyurethanes derived from aromatic isocyanates and used in this field of flooring application.
INTRODUCTION
Very recently the application of nanosilica in epoxy coatings has been reported [1]. Such epoxy-nanosilica composites were prepared using Bisphenol-A epoxy resin and SiO2 nanoparticles pretreated with a silane based coupling agent (3-Aminopropyltriethoxysilane) in order to increase the materials properties of the epoxy coating product such as tensile, elongation and abrasion resistance. Nanosized organic inorganic hybrid polymers (HP) with designed functionalisation to improve desired materials properties of those thermosets are highly appreciated and
1313
represent competitive products of multifunctional additives. Their preparation is based on a new technology concept developed at SINTEF [2-4]: HPs are appropriately modified by a suitable choice of starting compounds to improve commercial epoxy resins. The nanoparticle based dispersions are prepared by a sol-gel method. Such HPs are manufactured as amine modified nanoparticles (HAPS) in a size of 2-5 nm [5, 6] by controlled kinetics of the hydrolysis and the condensation reaction of 3-Aminopropyltriethoxysilane.
EXPERIMENTAL
Particle size determination. Particle size and size distribution were measured with a Nanosizer-ZS from Malvern Instruments Ltd. based on dynamic light scattering (DLS). Pendulum hardness. Film hardness was measured by König pendulum damping test. The pendulum hardness tester works on the principle of the damping time of a pendulum oscillating on the sample. The test was carried out at 23C and relative humidity 50 ± 5%. The test result is given as the number of oscillations for the amplitude to decrease from 6° to 3°. The amplitude of the oscillation reduces faster when the sample is soft and still not finally cured. Scratch resistance. Scratch resistance was measured by a Sheen scratch tester, according to ISO 1518. Pigmented films were applied on alumina-panels (150μm wft) and cured for 4 weeks. UV resistance. UV-resistance was correlated to results from gloss retention measured during exposure in a QUV-chamber. Gloss was measured by Triglossmaster (60; from Sheen). The transparent, unpigmented films were applied on primed alumina-panels (100μm wft).
RESULTSMaterials:Synthesis of HP. The nanoparticle based dispersions used in this paper are prepared by a sol-gel method [7]. The starting material is the hydrolysable amine functionalized trialkoxysilane 3-Aminopropyltriethoxysilane. Completion of silane hydrolysis and condensation reactions carried out in a glycol based solvent results in nanoparticles with amine groups (HAPS [6], Figure 1).
sol-gel nanoparticles with aminegroups (HAPS)
NH2 NH
2N H
2
N H2
N H2N H
2NH
2
NH2
NH2
NH2
SiO1.5NH
2 Si
OEt
OEtOEt
+ H2O
- EtOH
Figure 1: Synthesis of the organic inorganic hybrid polymer HAPS: controlled
sol-gel reaction of γ-APS resulting in nanoparticles with amine groups
14
In order to manufacture amine modified HP of a size of 2-5 nm (Fig. 2) it is required to establish chemical conditions that ensure a correct balance between the kinetics of the hydrolysis and the condensation reaction.
0
5
10
15
20
1 10 100 1000 10000
Volu
me
(%)
Size (d.nm)
Size Distribution by Volume
Figure 2: Size distribution of HAPS quality of HAPS measured by DLS
Selected epoxy resins. There are different epoxy grades used in this paper which are presented in Table 1. The epoxy components are based on a Bisphenol A backbone differing in the chain length (molecular weight) and π-system (hydrogenated derivate H.epoxy). The original formulations with epoxy coatings derived from solid epoxy (S.epoxy) and liquid epoxy (L.epoxy) with their corresponding hardener component are used as reference materials. Selected formulations on mixing these two types of resin are investigated and compared to the standard controls. Selected polyurethane qualities (aromatic based and aliphatic based) known to be used in the field of flooring and industrial applications are used as standards for the evaluation of materials properties of the modified epoxy formulations as well.
Table 1. Description of the various qualities of epoxy resins used in this paper
(MW = molecular weight)
Quality Resin-type Hardener-type S.epoxy Bisphenol A; high MW (900g/mole) Polyamide (pamine) L.epoxy Bisphenol A; low MW (380g/mole) Polyamineadduct (pamide) H.epoxy hydrogenated Bisphenol A (2200g/mole) polyamide / polyamineadduct PU arom 2-pack Polyurethane aromatic polyisocyanate PU aliph 2-pack Polyurethane aliphatic polyisocyanate
Mixing procedure and sample preparation. The hardener components of the different epoxy resins are modified by various amounts of added HAPS (replacement up to 50wt%). Stoichiometric mixing ratios were used. All components are mixed by moderate agitation The ready-to-handle resin is applied by tape casting on non-adherent polymer substrates, glass and primed metal substrates in different wet film thicknesses (= wft; varied from 200µm to 50µm, respectively). The very smooth coating layers are cured in a climate room, 23°C and 50±5% RH for at least 21 days before characterisation and testing.
1515
Characterisation and testing: The materials properties of the resin modifications are evaluated on the one hand by their curing rate with respect to hardening and on the other hand by their resistance to UV exposure concerning gloss retention. Curing rate. The evolution of hardness is determined on transparent, unpigmented films which are applied on a glass substrate by film casting with a wet film thickness (wft) of 100μm.
König pendulum hardness
0
20
40
60
80
100
120
140
160
1 day 4 days 1 week 2 weeks 3 weeks 4 weeks
curing time
[Num
ber o
f osc
.] S.epoxy +polyamideL.epoxy+polyamineH.epoxy+pamide/pamineH.epoxy+1wt% HAPSH.epoxy+1,8wt% HAPSPU aliph
Figure 3: Evolution of pendulum hardness with time for selected epoxy formulations
Figure 3 illustrates the curing rate of epoxy formulations from the hydrogenated epoxy resin modified with the multicrosslinking nanoparticle HAPS (addition of 1wt% and 1,8wt in stoichiometric relation) compared to the unmodified coating and to the standard epoxies (S.epoxy and L.epoxy). It can be seen that there is a tendency of increasing film hardness in the hydrogenated epoxy system due to modification with HAPS. Since the addition of 1,8wt% of HAPS results in some softer coating films than the addition of 1,0wt% it can be assumed that there will be an optimum concentration below 1,8wt% for the modified hydrogenated epoxy. This means that already a small amount of added aminofunctionalized nanoparticles leads to a detectable effect in the curing rate. In the epoxy resin “S.epoxy” increased film hardness with higher amounts of HAPS can be detected (figure 4). An addition of 8,7wt% causes a curing rate comparable to that what is detected for aliphatic polyurethane. However, a modification with 1,6wt% HAPS gives less curing when compared to the unmodified S.epoxy. The modification of “L.epoxy” with HAPS causes in any case minor curing rate shown by lower pendulum hardness. With 21,5wt% HAPS added to the formulation the coating layers remain as soft as it is detected for the aromatic polyurethane formulation used as a reference.
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König pendulum hardness
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[Num
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.]S. epoxy+polyamide
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PU aliph
PU arom
S.epoxy,1,6wt% HAPS
S.epoxy, 3,3wt% HAPS
L.epoxy, 8,0wt% HAPS
S.epoxy, 8,7wt% HAPS
L.epoxy, 21,5wt% HAPS
Figure 4: Evolution of pendulum hardness with time for selected epoxy formulations
at different modification level with HAPS
Resistance to UV. Materials resistance to UV irradiation as well as to abrasive forces are investigated. UV light can cause material degradation and surface alteration. Resistance to UV light is evaluated by gloss retention of the coating layers. It could be shown that UV resistance can be positively influenced by modifications with HAPS (figure 5). Higher crosslink density results in higher resistance to UV degradation at the coating surface.
QUV-chamber - gloss retention
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L.epoxy+polyamineL.epoxy, 8,0 wt% HAPSL.epoxy, 21,5 wt% HAPSPU aliphPU arom
Figure5: Evolution of gloss with exposure time to accelerated climatic conditions
In a longterm evaluation of modified L.epoxy resins a positive effect of HAPS addition becomes obvious. Compared to the unmodified resin the gloss retains for prolonged exposure periods as expected due to higher crosslink density for modified resins. Exposure periods of around 1000 hours at accelerated conditions can be
17
observed with gloss retention of 90% related to the original value at test start for the modification L.epoxy/21,5wt% HAPS. This implies that the lifetime of withstanding against UV initiated degradation effects resulting in gloss reduction can be prolonged by a doubled time interval. The gloss retention of modified H.epoxy is illustrated in figure 6. The gloss is stable for about 1620 hours under the test conditions – about factor 1.5 longer compared to the unmodified type. This period is reduced in presence of some amount of S.epoxy in that type of formulation (H.epoxy(75)/S.epoxy(25)+20eq%HAPS). However, the period is still obviously prolonged compared to the unmodified S.epoxy (loss of gloss starts already after about 500 hours).
QUV chamber - gloss retention
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0 256 490 752 1037 1314 1642 1904 1976 1999
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H epoxy and polyamide
PU aliph
S. epoxy + polyamide
H.epoxy(75)/S.epoxy(25)+20eq%HAPS
Figure 6: Evolution of gloss with exposure time to accelerated climatic conditions
Scratch resistance: The mechanical properties of the resin formulations are evaluated by Sheen scratch resistance on pigmented coating layers (figure 7).
Sheen Scratch resistance
0100020003000400050006000
H.epoxy, nonano
H.epoxy +0,7% HAPS
H.epoxy+1,4% HAPS
S.epoxy+polyamide
adduct
PU aliph
Load
[g]
befo
re p
enet
ratio
n th
roug
h fil
m
Figure 7: Scratch resistance for selected epoxy modifications evaluated by the Sheen method
The results show very clearly that the addition of multicrosslinking HAPS as reactive nano-additive increase the scratch resistance by factor twice (H.epoxy+1,4wt% HAPS) compared to the unmodified resin H.epoxy. This means also an increased resistance compared to the aliphatic polyurethane used for reference and standard which makes the modification of hydrogenated epoxy resins with nano-sized HAPS
18
interesting and promising for the introduction into the field of e.g. flooring and industrial applications.
SUMMARYThe aminofunctionalised organic inorganic hybrid polymers (HP) as multicrosslinking nanoparticles show a high potential of industrial importance and their application in selected thermosets (epoxies) is very efficiently. The fundamental principle of reactive additives is proofed to be very interesting and promising. Coordinated research and development along with patenting generates a basis for a large variety of various industrial applications with different requirements, presently developed and initiated for the future.
ACKNOWLEDGEMENT The author team would like to thank Jest Beylich, Britt Sommer, Kjell Windsland, Heidi B. Ingebretsen, Trine Nilsen and Inga Askestad for their contribution in sample preparation and characterization. The authors are thankful to the Norwegian Research Council for financial support.
REFERENCES [1] “Interpretation of Mechanical and Thermal Properties of Heavy Duty Epoxy Based Floor Coating Doped by Nanosilica”, M.M.A. Nikje, M. Khanmohammadi, A.B. Garmarudi, Nanotechnology in Construction 3 (2009) 163-167. [2] “Epoxy resin curing agent for enhanced wear resistance and weatherability of cured materials”, Ch.R. Simon, F. Männle, J. Beylich, R.H. Gaarder, K. Windsland, WO2004035675 (2004). [3] “Method for the manufacture of polybranched organic/ inorganic hybrid polymers”, Ch.R. Simon, F. Männle, j. Beylich, K. Redford, B. Sommer, E. Hinrichsen, E. Andreassen, K. Olafsen, T. Didriksen, WO2005100449 (2005), WO2005100450 (2005) WO2005100469 (2005). [4] “Light protective additive based on organic/inorganic hybridpolymer, method for its manufacture and use thereof”, K.R. Rodseth, F. Männle, WO2007053024 (2007). [5] „New Method for Improving Properties of Polymer Composites by Using Organic Inorganic Hybrid Polymers“, M. Pilz, F. Männle, Ch.R. Simon, S.L. Trevor, H. Bu, B.S. Tanem, Solid State Phenomena 151 (2009) 10-16. [6] “Multifunctional nanoparticles for high-performance binders”, J.Yang, Ch. R. Simon, F. Männle, M. Pilz, H. Bu, 19th SLF Congress 2009, Sandefjord, 6-9 September 2009. [7] C.J. Brinker and G.W. Scherer: Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing (Academic Press, San Diego, 1990), 97.
SPEAKER
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Monika Pilz (Dr. rer. nat., 1990) is trained as a chemist with PhD in organic and metal-organic chemistry and has experience in material research and product development from both, medium-sized chemical industry and research institution for applied science in Germany. She collaborated with project partners on both national and international levels. The different areas of her experimental material research within industrial and chemical R&D range from developing innovative hybrid coatings for industrial and conservation applications tailor-made by inorganic-organic copolymers through sol-gel processing over to creating and generating unique industrial formulations towards the requirements of the competitive market on reactive two-component resins from polyurethanes and epoxides. She started at SINTEF Materials and Chemistry in June 2007 as a research scientist in the Group of Functional Ceramics and Nanomaterials (FCNM) in the Department of Energy Conversion and Materials located at Oslo. Her main project activities are concerned on nanosized particles and capsules by sol-gel chemistry with functionalized surface characteristics for improving materials properties of nanocomposites. She takes actively part in the EU-COST action MP0701 2008-2012 as a MC member as well as the vice chair of WG1 - Nanoparticles and Interfaces.
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R2 Group and Alberding BoleyR2 Group extends cooperation with Alberdingk Boley in Scandinavia 2 Group has been selling Alberdingk Boley´s oil products in Denmark for decades.Thereby, the two companies have built a good and solid cooperation, which they have now decided to extend by including the sales of dispersions in all of Scandinavia.As of September 1st 2013 the trading and production com-pany R2 Group has entered into a partnership agreement with Alberdingk Boley in order to represent their entire product range of water-based dispersions in Denmark, Swe-den, and Norway.Commercial Director at R2 Group, Thomas L. Nielsen, ex-plains: ”Due to our long lasting cooperation we know that Alberdingk Boley guarantees an outstanding technical ser-vice and major reliability. Furthermore, due to Alberdingk Boley’s leadership in quality and technology the product range of water-based acrylic and polyurethane dispersions fits perfectly with our current product line and our growth strategy for the Nordic markets.”The growth strategy in the Nordics means that R2 Group is constantly looking for commercial employees with the right technical background, Thomas L. Nielsen adds.Johannes Leibl, Head of Sales for Dispersions at Alberd-ingk Boley, explains why R2 Group was chosen as repre-sentative for Scandinavia: ”We have been searching for the right strategic partner for the Scandinavian market and are convinced that R2 Group has the right drive and market knowledge which is needed to support Alberdingk Boley´schallenging growth strategy in Scandinavia. We work in line with the motto ”expect the unexpected” and are convinced that due to their experience and flexibility R2 Group willindeed live up to this .”Alberdingk Boley, headquartered in Krefeld, Germany, is a major producer of water-based acrylic and polyurethane dispersions for the coatings industry. The company has a long history from being an oil mill to becoming a global player in the market for water-based dispersions.To learn more visit our Websites www.alberdingk.com or www.r2group.eu
Süddeutsche Emulsions-Chemie GmbH
In September 2013, the Mannheim based chemical com-pany celebrates its 100th company anniversary. The family owned company in fourth generation, is man-aged by Dipl. Ing. Christian Kost and Dr. Michael Kost. Since the beginning, the company deals mainly with the production of waterborne emulsions and dispersions. The company started with cod liver oil emulsions which were
produced and sold for veterinary and human use. In 1939 first production of fat free raw materials for bakeries and confectioneries began. Due to our expertise Süddeutsches Emulsionswerk was the only company in Germany being able to homogenize fat-free bakery raw materials. Therefore, the production con-tinued during the war. Since 1955, we focus on the production of paraffin and wax emulsions, first for the paper and cardboard industry. In the late 70s development and production of waterborne wax additives for the paint and coatings sector started. This industry sector estimates the tailor-made wax addi-tives (brands: WÜKONIL, SÜDRANOL, LUBRANIL, MIKRONIL) to optimize surface properties, such as the improving of the water resistance, scratch resistance, block resistance or the sliding and uses the know-how of SEC to change from solvent-based systems to environmentally-friendly waterborne systems. Environmentally friendliness is not lip service to SEC. “The spirit of sustainability and our responsibility to the environment have been since decades a key function to us. We restrain consciously from organic solvents and manu-facture quality products only dispersed in water or just as powders,” says Christian Kost. Since many years, SEC is also active with water based wax specialties in concrete curings, release agents, wood-, leath-er- and glass sector. In 2010, the company started with the development and production of polymer dispersions which are used, for ex-ample, as a barrier for paper and cardboard, as well as wa-terborne heat-sealing dispersions for flexible packaging. In this sector of flexible packaging, among others, SEC prod-ucts are used as environmentally friendly bondings of milk packaging, confectionery, aluminum packaging, pharma-ceutical blister packs, and for security features. As a family owned, medium-sized company SEC focus heavily on customer orientation and flexibility. Demands from the customers are followed by an uncomplicated and pragmatic approach and quickly realized by a flat manage-ment structure. From Mannheim, the company exports to 50 countries, mainly Europe and Asia. For this purpose, we make sure that our local sales partner understand the business of our customers and are competent, local contacts. Thanks to our logistics expertise, we deliver from Germany “just in time” - even in winter when our waterborne disper-sions have to be transported in heated vehicles. “With the experience of 100 years we want to continue to develop innovative waterborne wax emulsions and water-borne polymer dispersions in the future that provide value to our customers and create competitive advantages in the evolving market for water-based coatings,” says Dr. Michael Kost.
Industrinyt
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Coatingsad.indd 1 2012-07-31 14:13:36
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Titandioxid-extenders DispergermedelKaoliner med hög vithet EmulgatorerKalcinerad kaolin Delaminerad kaolin VätmedelSilika – Silikater Fluortensider SkumdämpareModifierade silikasoler ATH, AluminiumhydroxidFörtjockningsmedel Magnesiumhydroxid ZinkboratFree flowing agents Expanderbar grafit MolybdaterPigment Melamin –cyanuratRostskyddspigment - fosfat – boratGlasmikrosfärer PolyolerKeramiska mikrosfärer Fettsyror Dimersyror
Kemi-Intressen AB, Box 2018, 169 02 Solna, SverigeTelefon +46 8 629 63 30 Fax +46 8 529 63 35www.kemiintressen.com
Minerals & extenders
• kaolin• calcium carbonate• mica• microspheres
Additives
• biocides• siccatives• coalescents• micronized waxes• plasticizers• silicones• rheology modifiers• defoamers
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• alkyds, acrylics, epoxy• PVA, PVB and PVC-resins• CAB, CAP• silicon resins• polyols
Pigments
• TiO2
• iron oxides• effect pigments
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