Boya ve Kaplamalarda 3M™ Seramik ve Ici Bos Cam Mikrokurecikler

Transkript

3M Advanced Materials Division
Boya ve Kaplamalarda 3M Seramik ve Ici Bos Cam Mikrokurecikler
Kasim 2014
© 2014 3M. All Rights Reserved
Iletisim Bilgileri
Satis
Gonca Kozluca Can | Sr. Sales Representative
3M Turkey, Topcu Yuzbasi Sinan Eroglu Cad. Akel Is Merkezi No:6 Kavacık |
Istanbul Turkey
Office: +90 216 538 0777 | Mobile: +90 534 881 6613
[email protected] | www.3M.com | www.3mendustriyelcozumler.com
Zafer Kasikara | Country Business Leader / Ülke Direktörü
Industrial Business Group (IBG)
3M Turkey, Topcu Yuzbasi Sinan Eroglu Cad. Akel Is Merkezi No:6 - Kavacık |
34805 Istanbul, TURKEY
Office: +90 216 538 06 16 | Mobile: +90 532 424 42 13
[email protected] | www.3M.com
Ersin Kurtoglu | Business Development Manager
Advanced Materials Division, Central & East Europe
Topçu Yüzbaşı Sinan Eroğlu cad., Akel İş Merkezi No:6 A Blok | 34805 Kavacık
Beykoz / İstanbul / Turkey
Office: 90 216 538 0622 | Mobile: 90 533 501 2230 | Fax: 90 216 538 0788
Louis J. Lundberg | Global Business Manager, Specialty Additives
3M Oakdale, 6744 33rd Street North | Oakdale, MN 55128 USA
Office: 651 733 7440 | Mobile: 651 338 7473
© 3M 2013 All Rights Reserved.
Teknik
Boya Uygulama Gelistirme (USA)
Terri Shefelbine, Ph.D. | Research Specialist
3M Center, 236-2A-07, St. Paul, MN 55144 USA
Tel: 651-737-5099 Fax: 651-737-7686
Kevin J. Rink | Senior Technical Service Chemist
3M Center, Building 236-2A-07 | St. Paul, MN 55144 USA
Office: 651 737 1254 | Triminet: 8 737 1254 mobile:651-968-9774
Global Teknik Servis
Baris Yalcin, Ph.D. | Product Development Specialist
3M Center, 236-0G-B68 | St. Paul, MN, 55144-1000
Office: 651 733 6959 | Mobile: 651 387 1460 | Fax: 651 736 7794
Part 1: SERAMIK MIKROKURECIKLER
3
 3M™ Seramik Mikrokurecikler benzersiz, yari saydam, ince
parcacik boyutlu ve yuksek mukavemetli seramik mikrosferlerdir.
Bu mikrosferler boya performansini, kati oranini ve islenebilirligini
arttirmak icin tasarlanmistir.
Behr, Akzo Nobel, Sherwin-Williams, Hirshfield’s,
Benjamin Moore, Comex, Lanco, 4 Seasons, Lanco,
ACE, Kansai, Olympic PPG
4
3M ™ Ceramic Microspheres Products
Malzeme
Ezilme
Dayanimi
Properties
Gercek
Yogunluk
Yogunluk
Tane iriliği (microns)
Renk
Kutle(Bulk)
Yogunluk
Median Effective
Top Size
Unaided
Eye
Whiteness
(“L “value)
Kodu
90% Survival
(psi)
g/cc
W-210
W-410
W-610
>60,000
>60,000
>60,000
2.4
2.4
2.4
3
4
10
12
24
40
White
White
White
Ezilme
Dayanimi
pH
Sertlik
Yumusama
Noktasi
Kirilma
Endeksi
Dielektrik Sabiti
5
W-410
Test
Method
2.4 g/cc
(20.0 lbs/gal)
1.5 g/cc
(12.6 lbs/gal)
95 +
(Hunter L,a,b scale)
> 4,200 kg/cm²
( >60,000 psi)
9.0 – 12.0
6
1,020 °C
(1,870 °F)
1.53
ASTM D
2244
ASTN E
70
Mohs
Scale
Becke
Line
3.19
UV Isin
Gecirimi
UV Transparent
down to 250 nm
Isi
Iletkenligi
2.3 W/mK
Seramik ve Ici bos cam kureciklerin boya uretimine giris noktasi
Ilk Karistirma
ve dispersiyon
Alt Ilave
6
•
•
•
•
•
•
•
•
•
•
Su
Biositler
Co-Solvent (glycols)
Disperzant (islaticilar)
Kopuk Kesiciler
Surfaktant
Co-disperzant and Neutralizing agent
Kalinlastiricilar , Vizkosite ayarlayicilar
Titan
Dolgu Maddeleri (e.g. Kalsit, Kaolin, Nepheline Syenite, Seramik Mikrokurecikler)
•
•
•
•
•
•
•
•
•
Baglayici
Coalescing Aid
Es-cozucu (co-solvent)
Su
Kalinlastiricilar , Vizkosite ayarlayicilar
Kopuk Kesiciler
Surfactant
Asitlik Gidericiler , pH ayari
Hassas Dolgu maddeleri (cam kureler)
• Weight Solids
• Volume Solids
• CPVC
• PVC
Seramik Mikrokureciklerin diger dolgu maddeleri ile morfolojik
karsilastirilmasi ve Dekoratif Boyalara Etkileri
Nepheline Syenite
Kaolen
Kalsit
Formul
― Su Bazli Mat (Flat) Akrilik Dekoratif Boya (40% PVC)
Seramik Mikrokurecikler (CM)
-Daha dusuk yuzey alani
-Daha Dusuk Binder (tutkal) gereksinim
- Ayni PVC de daha dusuk viskosite
― Diger dolgu malzemelerinin orani bozdurulmadan giderek azaltilarak 3 ayri seramik
mikrokurecik dolgu miktari olusturuldu
7
Boya Hazirlama Metodu
1) Ilk Karistirma ve Dispersiyon
•
•
•
•
Yüksek Devirli Karıştırıcı (Cowles blade)
Su, tum dolgu maddeleri, titan, ve katki maddeleri
20 dakika at 1600 rpm.
Dispersiyon Controlu Fineness of Grind
http://www.youtube.com/watch?v=F8UPHqe0040
2) Alt ilave
Karistirici with axial flow propeller blade
Akrilik Baglayici, Coalescent, Köpük
Kesiciler, Fungusitler ve Kalinlastiricilar
http://www.youtube.com/watch?v=zS0YZ7Vkb3Q
8
Flat architectural
formulation
Material
Ingredient
Nephyline syenite
: Calcium carbonate = ~1
: Calcined kaolin clay=~1.5
Nephyline syenite, Calcined kaolin clay, and
calcium carbonate removed in equal volume to
ceramic microspheres added.
Potassium tripolyphosphate
Triton ™ CF-10
Rhodaline ® 643
Skane ™ M8
Ti-Pure ® R-706
Eagle Zinc 417
Minex ® 4
Iceberg ®
Duramite ®
3M ™ Ceramic microspheres
Attagel ® 50
Rhoplex ™ VSR-50
Rhodaline ® 643
Texanol ™
Propylene glycol
9
5 Vol%
Ceramic
10 Vol%
Ceramic
Grind
Natrosol ® 250 MHR
water
Tamol ™ 851
Volumes
Nephyline syenite
No Ceramic
Density Microspher 2.5 Vol%
(lbs/gallon)
es
Ceramic
Acrysol ™ NPR 2020
TOTALS
Selulozik Kalinlastirici
Su (Water)
Islatici (Dispersant)
11.5
8.34
9.9
0.23
29.58
1.07
0.31
29.31
1.05
0.23
29.72
1.06
0.31
29.34
1.05
Buffer
Surfaktant
Degasser
Biositler
21.15
8.97
7.09
8.6
0.08
0.26
0.14
0.27
0.07
0.26
0.15
0.26
0.07
0.26
0.15
0.42
0.07
0.26
0.15
0.26
TiO2
Zinc oxide
Nephyline Syenite
Kaolen
Kalsit
Seramik
Mikrokurecikler
Clay
33.4
46.7
21.7
21.93
22.7
5.53
0.57
4.50
2.97
4.30
5.50
0.56
3.51
2.32
3.52
5.49
0.56
2.57
1.70
2.45
5.50
0.56
0.66
0.43
0.66
20
19.7
0.00
0.27
2.54
0.26
5.08
0.27
10.16
0.26
8.8
7.09
7.92
8.63
47.08
0.53
1.26
0.79
47.20
0.53
1.25
0.79
46.81
0.53
1.25
0.79
47.13
0.53
1.25
0.79
8.67
0.59
100.00
0.62
100.00
Let Down
100% Akrilik Baglayici
Degasser
Coalescent
Coalescent
Non-iyonik urethan
kalınlaştırıcı
Total (Volume)
© 20130.61
3M. All Rights Reserved
0.61
100.00
100.00
Boya Testleri
 Asindirma and Parlatma Direnci
― Vinil Klorür / Asetat Kopolimer paneller (Laneta)
― 0.18-mm (7.0-mil) film aplikatoruen
Test Adi
Metod
Dispersiyon
Olcumu- HegmanTipi Olcer
D-1210
Spekuler Gloss
ASTM D 523
Tri-gloss meter
ASTM D 6736
600 g bir ağırlık kullanılmıştır ve parlaklık 20, 50
ve 100 geçişten sonra ölçüldü.
Elcometer ® 1720 aşınma test cihazı
4 testin ortalaması
(Panel basina 2 test ve 2 panel test edilmistir)
Asindirma Direnci
(Scrub
Resistance)
ASTM D 2486
Hassas Ovma Scotch-Brite ™ pedi
fırça tabanına bağlandi ve
standart aşındırıcı ovma malzemesi kullanıldı
Elcometer ®1720 Aşınma Test Cihazı
4 testin ortalaması
(Panel basina 2 test ve 2 panel test edilmistir)
Opaklik (Opacity)
Kontrast Orani
Opaklık (Y) = (Y-siyah arka / Y-beyaz arka) x 100
Renk Flex EZ spektrofotometre örneklerin
opaklığını belirlemek için kullanılmıştır
― Paneller, 7 gün boyunca yatay olarak havayla kurutulmuştur Kumas Ovma ile
― Kalinlik 50 mikron +/- 5 mikron
― 1720 Elcometer aşınma test cihazı kullanılır
 Parlaklik Panelleri
― 3B sealed opacity charts (Leneta)
― 3 bird mil gauge film applicator.
Parlatma Direci
(Burnish
Resistance)
― Panels were air-dried completely.
10
Değişiklikler
Sonuclar: Hegman Ezilme Inceligi
8
7
Hegman Units
6
5
4
12 um Top Size
W-210
24 um Top Size
W-410
3
40 um Top Size
W-610
No Ceramic Microspheres
2
1
0
0,00%
2,00%
4,00%
6,00%
8,00%
10,00%
12,00%
Volume Percent Ceramic Microspheres
Kucuk partikul boyutlu seramik mikrokurelerle artan yukleme ile ezilme numarasi artis gostermektedir
Buyuk partikul boyutlu seramik mikrokurelerle artan yukleme ile ezilme numarasi dusus gostermektedir
11
http://www.youtube.com/watch?v=qZ8J6hK4TuA
Sonuclar: Parlaklik at 85 º (Gloss Derecesi)
6
85 Deg Gloss
5
4
3
12 um Top Size
W-210
24 um Top Size
W-410
40 um Top Size
2
W-610
Tri-gloss meter
No Ceramic Microspheres
1
0
0,00%
2,00%
4,00%
6,00%
8,00%
10,00%
12,00%
Volume Percent Ceramic Microspheres
Kucuk Partikul boyutlu seramik mikrokureler artan yukleme ile gloss artisi gosterir
Buyuk Partikul boyutlu seramik mikrokureler artan yukleme ile gloss azalisi gosterir
12
http://www.youtube.com/watch?v=iktaX-9h6nM
BOYA TESTI– KUMAS OVMA ILE PARLATMAYA DIRENCI (BURNISH RESISTANCE-D6736)
http://www.youtube.com/watch?v=raeRhcmADhs
Interior flat paints may become burnished in areas
where clothing or upholstered furniture rub against a
wall. This rubbing may cause a smoother, glossier
surface at the contacted area, depending on the
level or type of pigments in the paint and binder
hardness. This method permits a more quantitative
estimate of burnish resistance than those using
manual rubbing techniques.
A weight of 600 g was used and the
gloss was measured after 20, 50, and
100 passes.
Elcometer ® 1720 abrasion tester
Average of 4 tests
(2 tests per panels x 2 panels)
Measure of the increase in gloss after rubbing a paint surface per ASTM #D673608. For flat paints we do not want the gloss to change.
600 g
Elcometer ® 1720 abrasion tester
13
4 ply cotton mesh
Sonuclar: Kumas Ovma ile Parlaklik % degisimi (85 º gloss) 100 gecis)
Seramik mikrokuresiz
105% 85 º gloss artisi
Buyuk partikul boyutu ve yukleme miktarinda artis daha dusuk parklaklik degisimine neden olur ( % 85 º gloss degisimi).
14
Sonuclar: Asindirma Direnci (Ovma testi)
Seramik Mikrokuresiz
903 gecis
Yukleme miktarindaki artis ve buyuk partukul boyutlu seramik mikrokureler
boya filminin asinma direncini arttiriyor.
15
Ozet: Seramik Mikrokureler
Hacimce% 10 mikro-küreciklerin kontrol formülasyonuna karşılaştırılmasi
16
Top Size (um)
Gloss
Azalmasi
Gloss
Artmasi
Donukluk
(Opacity)
Kumas Ovma ile
Parlaklik Direnci
(Burnish
Resistance)
Ovma ile
Asindirma
Direnci
(Scrub
Resistance)
Hand feel
12
-
+
-
++
++
Much smoother
24
=
=
-
++
++
Smoother
40
+
-
-
+++
+++
Rougher
Sonuclar: Seramik Mikrokurecikler
 Ovma (asindirma) ve burnish (parlatma) direnci seramik mikrokure
yukleme miktari ve daha buyuk partukul boyutu ile gelistirilebilinir.
 Parlaklik derecesi (Gloss) ve ezilme inceligi ( Hegman gage) partikul
boyutu ile artar
 Hacimce % 5-10 iyi bir baslangic yukleme miktaridir
 Seramik mikrokure optimal yukleme miktari deneylerle tespit edilmelidir.
17
Şekil ve Sertlik
 Sertlik ve küresel şekil kumas ovma ile
parlaklik artma direncinin artmasına
katkıda bulunur
18
 Yumusak ve kenarli partukullerden
olusan siradan dolgular boya
yuzeyinden kolay kopar
Bolum 1: Formülasyon yaklaşımi /
fayda optimizasyonu- Akrilik Boya
19
Pigment Hacim Konsantrasyonu (Pigment Volume Concentration)
PVC 
Vb = Baglayici (binder) hacimi, kuru
Vp = Pigment Hacimi
Ve = Dolgu Maddesi Hacimi
20
V p  Ve
Vb  Ve  V p
*100
PVC : pigment ve dolgu maddelerinin kuru boya filime orani
© 2014
3M.3M.
AllAllRights
Reserved.
© 2013
Rights Reserved
Kritik Pigment Hacim Konsantrasyonu (Critical Pigment Volume
Concentration) (c-PVC)
Below c-PVC, there is more
than enough binder to wet
the fillers and fill the spaces
between fillers.
21
At c-PVC, there is just
enough binder to wet
between fillers.
Above c-PVC, there is not
enough binder to wet
between fillers. Voids form.
© 2014
3M.3M.
AllAllRights
Reserved.
© 2013
Rights Reserved
C-PVC Etkileyen Faktörlerin Bazılari
Bağlayıcın parçacık boyutu ve dağılımı
Baglayicinin dolgulari islatmasi
Bağlayıcı koalesansi (cam geçiş sıcaklığı Tg )
Dolgu maddesi taneciğinin büyüklüğü ve dağılımı
Dolgu yüzey alanı.
Dolgular göreceli boyutları.
3M ™ Seramik Mikrokürelerin bu özellikleri
c-PVC yi etkileyebilir.
c-PVC belirli bir bağlayıcı ve dolgu maddeleri karisimi icin deneysel olarak tespit edilir
22
© 2014
3M.3M.
AllAllRights
Reserved.
© 2013
Rights Reserved
Boya Formulasyonunda Etkenler
Performans
Dusuk PVC = daha iyi dayaniklilik
Dusuk PVC
Maliyet
Baglayici ve pigmentler genelde pahali iceriklerdir
VOC uçucu organik içerik regulasyonu
Sifir VOC’ye gidis
Yeni ve daha az baglayici kullanimi
Performans
cPVC ustunde daha iyi ortuculuk elde edilir
Yuksek PVC
Ne kadar yuksek PVC li formulasyon yapilip performans dayanikliligi gosterilebilinir ?
23
© 2014
3M.3M.
AllAllRights
Reserved.
© 2013
Rights Reserved
Raw Material Costs of Paint
Ingredient
Water added
TiO2
Resin dispersion
Fillers
Additives (rheology
modifiers, surfactants,
defoamers, biocides)
Totals
$/lb
2
1.85
0.14
2
Density
volume % in Cost $/100
(lb/gallon) $/gallon paint can
gallons
8.35
0.002
33.11
0.07
33.40
66.80
5.72
382.10
8.80
16.28
43.44
707.20
21.00
2.94
12.73
37.43
8.30
16.60
5.00
100.00
83.00
1209.79
% Cost
0%
32%
58%
3%
7%
Orta PVC’li bir boyada, baglayici ve
Titan genelde en fazla maliyet yaratan
iceriklerdir.
Using ceramic microspheres to
maintain physical properties while
increasing PVC can provide value to
the coatings formulator.
All values are estimates for illustration purposes.
24
3M Confidential.
© 2014
3M.3M.
AllAllRights
Reserved.
© 2013
Rights Reserved
PVC ‘ye gore Boya Fonksiyonlari
Boya cizilmeye baslayana kadar ovma testi
1200
Ovma testi naylon fircaya
ilistirilmis hassas Scotch-brite™
pedi ile yapilmistir
Gecis Sayisi
1000
800
TiO2 and calcined
kaolin clay
600
Yüksek sayı daha iyidir.
400
Rhoplex™ VSR-50 baglayici ile yapilmis boya, 100% akrilik resin
Dolgularin Hacimce % 31 TiO2, gerisi calcined kaolin clay
200
0
0
20
40
60
80
PVC
25
© 2014
3M.3M.
AllAllRights
Reserved.
© 2013
Rights Reserved
PVC ‘ye gore Boya Fonksiyonlari
Boya cizilmeye baslayana kadar ovma testi
1600
For 3M™ W-410 ceramic microspheres,
scrubs go up compared to calcined kaolin
clay
1400
Gecis Sayisi
1200
1000
TiO2 and calcined kaolin clay
800
TiO2, calcined kaolin clay, and 3M W410 ceramic microspheres
600
400
200
0
0
26
50
PVC
Paint made with Rhoplex™ VSR-50
31 vol. % of fillers is TiO2
45 vol. % of fillers is 3M™ W-410 Ceramic
Microspheres
100
© 2014
3M.3M.
AllAllRights
Reserved.
© 2013
Rights Reserved
W-410 in a Flat Paint
27
Mat Akrilik Su Bazli Boya Formulu
DG-1 Formulation
GRIND
Water
Tamol 850
Potassium trypoliphosphate
Triton™ CF-10
Rhodoline ®643
Ti-pure® R-706
Eagle Zinc 417 W (Alfa Aesar 99.99%, 200 mesh
Minex® 4
Iceberg®
Duramite®
3M™Ceramic W-410
Attagel® 50
Skane™ M-8
Natrosol® 250 MHR (2.5% in water)*
LET DOWN
Texanol™
Propylene Glycol
RHOPLEX™ VSR-50
Rhodoline® 643
Acrysol™ RM-2020NPR
Density =11.80 lbs/gal
PVC = 40 %
28
Pounds
95.61
7.06
1.06
1.54
0.70
123.35
17.62
65.29
43.53
65.29
0.00
3.52
1.52
71.01
6.64
4.57
276.90
2.50
12.27
Gallons
11.45
0.70
0.05
0.18
0.10
3.69
0.37
3.00
1.98
3.01
0.00
0.18
0.18
8.46
0.84
0.53
31.29
0.35
1.41
Volume adjustments made in
Nephylene syenite (Minex ® 4)
Calcium carbonate ( Duramite ®)
Calcined aluminium silicate
(Iceberg ®) to add ceramic
microspheres.
Formula
Code
% V/V
3M™Additive
PVC
DG-1
0.0
40
DG-2
2.5
41
DG-3
5.0
40
DG-4
10
40
DG-5
15
49
DG-6
20
56
Paint Testing
 Washability, Scrub and Burnish Resistance
― Vinyl Chloride/Acetate Copolymer panels (Leneta)
― 0.18-mm (7.0-mil) clearance film applicator.
― Panels were air-dried in a horizontal position for 7 days,
prior testing.
 Opacity Panels
Test Name
Method
Fineness of
Grind by
Hegman-Type
Gauge
D-1210
Specular Gloss
ASTM D 523
Burnish
Resistance
ASTM D 6736
Scrub
Resistance
ASTM D 2486
Test method A
1)
A shim of 0.5 mm was
used instead of a 0.25 mm
2)
A non scratch Scotch-brite ™
pad was attached to the bottom
of the brush and standard
abrasive scrubbing media was
used as indicated in the ASTM.
Washability
ASTM D-4828
Blue paper Mate® pen was used
Lines were cleaned, until they
were not visually seen; the
number of passes were recorded
at that point.
― 3B sealed opacity charts (Leneta)
― 3 bird mil gauge film applicator.
― Panels were air-dried completely.
29
Modifications
Viscosity of Ceramic Microsphere Level Study Paints
Formula
30
Volume % of
W-410
Initial Viscosity
(KU)
Viscosity @
3 days
Viscosity
after 7days
DG-1
0
94.0
95.6
95.5
DG-2
2.5
94.6
95.2
95.0
DG-3
5.0
96.8
97.4
97.2
DG-4
10
96.0
97.8
97.5
DG-5
15
94.7
96.4
96.5
DG-6
20
94.0
96.1
96.3
Number of Cylces
Addition of W-410 Ceramic Microspheres: Effect on Washability
450
400
350
300
250
200
150
100
50
0
Washability
PVC: 40
PVC: 49
PVC: 41
PVC: 40
PVC: 40
0
2,5
PVC: 56
5
10
W-410 volume (%)
Lower the better
15
20
Note: 15 and 20 % W-410 have PVC=49 and 56
31
Addition of W-410 Ceramic Microspheres: Effect on Scrubability
Scrub Resistance
1200
1000
Number of Cycles
Higher cycles the better
PVC: 40
800
PVC: 41
PVC: 40
600
400
PVC: 49
PVC: 56
PVC: 40
200
0
0
2,5
5
10
W-410 volume (%)
15
20
Note: 15 and 20 %W-410 have PVC=49 and 56
32
Addition of W-410 Ceramic Microspheres: Effect on Burnish Resistance
70
Burnish Resistance
PVC: 40
PVC: 41
PVC: 40
60
Percentage (%)
Burnish Resistance 60
Burnsih Resistance 85
50
PVC: 49
PVC: 56
PVC: 40
40
30
20
10
0
0
2,5
5
10
W-410 Volume (%)
15
20
Note: 15 and 20 %W-410 have PVC=49 and 56
33
Addition of Ceramic W-410 and its Effect on Opacity
OPACITY
97,5
PVC: 56
Percentage (%)
97
96,5
PVC: 40
PVC: 41
96
PVC: 49
PVC: 40
PVC: 40
95,5
95
0
34
2,5
5
10
W-410 Volume (%)
15
20
Conclusions
 Addition of W-410 3M™ Ceramic Microspheres considerably increases the performance of an acrylic
water-based paint, thus increasing the paint’s quality.
 Addition of 5% by volume of W-410 to a water-based acrylic paint formulation with PVC of 40%, yields the
best performance
 Higher loading of 15-20 percent by volume of W-410 3M™ ceramic microspheres is possible when
increasing the PVC content to while reducing the amount of resin, and yet still exhibits a higher
performance when compared to the baseline formulation which has no W-410.
 Viscosity did not increase dramatically when high loadings of W-410 were added to the water based paint
formulations in this study.
35
Considerations
 High loadings (10-20% by volume) of W-410 may be possible to add to a baseline water-based flat
architectural paint with PVC of 40%, if the majority of its fillers are substituted with W-410 ceramic
microspheres; as is the case of formulas DG-5 and DG-6 in this study
 Addition of W-410 Ceramic Microspheres with low to medium loading (2.5-10% volume) slightly decreases
opacity in a flat architectural paint; as compared to the baseline paint formulation with no ceramic
microspheres added and similar PVC content
 Higher loadings (10-20 percent) of W-410 will increase opacity, as the PVC increases, even if other fillers
are present in very low amounts.
36
Bolum 2: Ici Bos Cam Kureler
(Glass bubbles)
37
 3M ™ ici bos cam kurecikler su dayanıklı ve kimyasal olarak stabil bir
soda-kireç borosilikat camdan yapılmış pürüzsüz küresel içi boş
parçacıklardır. Bu kurecikler, yüksek mukavemetli olup, termoplastik,
termoset, elastomerler, boyalar, kaplamalar ve yapıştırıcı uygulamalarinda
kullanılan düşük yoğunluklu katkı maddeleridir.
38
Glass Bubbles and Ceramic Microspheres Tested
Particle Size Distribution, Microns by volume 3M QCM 193.2
Additive Target Crush Strength True Density
Code
(90% survival)
(g/cc)
10% microns 50% microns
K1
250
0.125
30
65
K15
300
0.15
30
60
S22
400
0.22
20
35
K25
750
0.25
25
55
S32
2000
0.32
20
40
K37
3000
0.37
20
45
XLD3000
3000
0.23
15
30
S38HS
5500
0.38
15
44
K46
6000
0.46
15
40
K42HS
7500
0.42
11
22
S60
10000
0.6
15
30
iM16k
16000
0.46
12
20
S60HS
18000
0.6
11
30
iM30k
28000
0.6
9
16
W410
60000
2.4
1
4
39
90% microns
115
105
65
90
75
80
40
75
70
37
55
30
50
25
15
95% microns
120
115
65
105
80
85
85
80
42
65
40
60
27
24
Thermal conductivity of 3M™ Glass Bubbles
Select from 3M’s product portfolio to obtain desired K Value.
40
K1
K15
0.125
0.15
250
300
0.113
0.117
K20
0.20
500
0.126
Mat Akrilik Su Bazli Boya Formulu
DG-1 Formulation
GRIND
Water
Tamol 850
Potassium trypoliphosphate
Triton™ CF-10
Rhodoline ®643
Ti-pure® R-706
Eagle Zinc 417 W (Alfa Aesar 99.99%, 200 mesh
Minex® 4
Iceberg®
Duramite®
3M™Ceramic W-410, 3M™Glass Bubble
Attagel® 50
Skane™ M-8
Natrosol® 250 MHR (2.5% in water)*
LET DOWN
Texanol™
Propylene Glycol
RHOPLEX™ VSR-50
Rhodoline® 643
Acrysol™ RM-2020NPR
Density =11.80 lbs/gal
PVC = 40 %
41
Pounds
95.61
7.06
1.06
1.54
0.70
123.35
17.62
65.29
43.53
65.29
0.00
3.52
1.52
71.01
6.64
4.57
276.90
2.50
12.27
Gallons
11.45
0.70
0.05
0.18
0.10
3.69
0.37
3.00
1.98
3.01
0.00
0.18
0.18
8.46
Volume adjustments made in
Nephylene syenite (Minex ® 4)
Calcium carbonate ( Duramite ®)
Calcined aluminium silicate
(Iceberg ®) to add ceramic
microspheres or GBs.
Formula Code
% V/V
3M™Additive
PVC
DG-1-Baseline
0.0
40
DG-3
5.0
40
0.84
0.53
31.29
0.35
1.41
Glass Bubbles: Effect of Grade on Washability
# Passes to remove pen line
Washability
700
600
500
400
300
200
100
0
Lower the better
5 vol % glass bubbles in all paint formulations
42
Glass Bubbles: Effect of Grade on Scrubability
# Passes to paint failure
Scrubability
Higher the better
1200
1000
800
600
400
200
0
43
Glass Bubbles: Effect of Grade on Opacity
Opacity (%)
Opacity
Higher the better
98
97,5
97
96,5
96
95,5
95
94,5
44
Glass Bubbles: Effect of Grade on Gloss
85 º Gloss
3,5
85 º Gloss (GU)
3
2,5
2
1,5
1
0,5
0
45
46
Additive Code
Reduce Glossiness
Opacity
Scrub Resistance
W-410
+ ( compared to glass bubbles
for this study)
+( compared to glass
bubbles for this study)
++++
iM30K
+
++
++++
S60HS
+++
++++
+++
K46
++++
++++
+++
S60
+++
++++
+++
iM16K
++
+
+++
K42HS
+++
++
++
S38HS
++++
++++
++
XLD3000
+++
+++
+
K37
++++
++++
+
S32
++++
++++
+
S22
++++
+++
+
K25
++++
+++
NSI
K15
++++
+
NSI
K1
++++
+
NSI
3M Confidential – Internal Use Only
+
fair
++
moderate
+++ good
++++ excellent
NSI not significant
increase
Conclusions: Glass Bubbles in Architectural Paint
 Glass bubbles can increase opacity over conventional fillers and ceramic
microspheres, depending on grade.
 Stronger glass bubbles improve scrubability more than lower strength bubbles.
 Glass bubbles do not improve washability over conventional fillers.
 Glass bubbles decrease gloss more than smaller ceramic microspheres.
47
Part 2: Cost-in-use of Glass
bubbles
48
3M™ Glass Bubbles in Acrylic Paint
 Acrylic binder at 45 PVC
 Remove TiO2 and substitute equal volume
of 3M™ Glass Bubbles iM16K
 Formulation goal: maintain scrub properties
and decrease cost without lowering opacity
49
3M Confidential.
© 2014
3M.3M.
AllAllRights
Reserved.
© 2013
Rights Reserved
Formulations
Material
50
PVC = 45, Grind = 5.5
Viscosity = 95–105 KUs
Base Amount
WPG
(lbs)
Amount
(gal)
Amount (gal)
Control
Formula A:
No glass bubbles
Formula B:
Replace 5 wt% TiO2
with iM16K
Formula C:
Formula D:
Replace15 wt% TiO2 Replace 15 wt% TiO2
with iM16K
with other fillers
Water
Tamol™ 851
Potassium tripolyphosphate
Triton™ CF-10
Skane™ M8
Rhodaline® 643
Natrosol® 250 HR
Ti-Pure® R-706
Eagle Zinc 417
Minex® 4
Iceberg®
Duramite®
3M™ Ceramic Microspheres
W-410
Attagel® 50
246.87
10.57
1.62
2.32
2.30
1.02
1.81
184.68
26.42
97.83
65.19
97.74
8.34
9.90
21.15
8.97
8.60
7.09
11.50
33.40
46.70
21.70
21.93
22.70
29.60
1.07
0.08
0.26
0.27
0.14
0.16
5.53
0.57
4.51
2.97
4.31
29.60
1.07
0.08
0.26
0.27
0.14
0.16
5.53
0.57
4.51
2.97
4.31
29.8
1.06
0.07
0.26
0.27
0.15
0.23
5.5
0.55
2.57
1.7
2.46
29.8
1.06
0.07
0.26
0.27
0.15
0.23
5.23
0.56
2.57
1.7
2.46
29.8
1.06
0.07
0.26
0.27
0.15
0.23
4.68
0.56
2.57
1.7
2.46
29.3
1.05
0.07
0.26
0.26
0.15
0.23
4.6
0.55
2.81
1.95
2.68
0.00
20.00
0.00
0.00
5
5
5.09
5.0
5.28
19.70
0.27
0.27
0.27
0.27
0.27
Rhoplex™ VSR-50
Rhodaline® 643
Texanol™
Propylene glycol
3M™ Glass Bubbles iM16K
414.57
3.75
9.97
6.82
8.80
7.09
7.92
8.63
3.84
47.11
0.53
1.26
0.79
47
0.53
1.25
0.79
0.28
47
0.53
1.25
0.79
0.83
47.8
0.52
1.23
0.78
0
Acrysol™ NPR 2020
TOTALS
5.13
1183.87
8.67
0.59
100.00
0.52
100.00
0.44
100.01
0.5
100.00
3M Confidential.
0.27
Mix let down 10 min
47.11
47
0.53
0.53
1.26
1.25
0.79
0.79
0.00
0
Add to 95-100 KU
0.59
0.58
100.00
100.04
© 2014
3M.3M.
AllAllRights
Reserved.
© 2013
Rights Reserved
Density of paint decreases with addition of glass bubbles
Weight per gallon of paint when TiO2 is replaced by 3M™ Glass Bubbles iM16K
11,8
11,7
100% acrylic
flat paint
11,68
WPG
Lbs/gallon
11,6
11,5
11,44
11,4
Weight per gallon
of paint
11,36
11,3
11,2
11,1
0
5
10
15
20
25
wt% TiO2 replaced
51
3M Confidential.
© 2014
3M.3M.
AllAllRights
Reserved.
© 2013
Rights Reserved
Cost Exercise: TiO2 replacement by volume
Cost savings/gallon of paint by replacing TiO2 with equal
volumes of 3M™ Glass Bubbles iM16K
0,7
Cost Savings $/gallon
iM16K for TiO2
Formulation C has 15 wt% less TiO2
than Formulation A. This equates to
about 0.83 gal of TiO2. At $2/lb, this is
about $55 in savings for 100 gallons
100% Acrylic
Flat Paint
0,6
0,5
Replacing TiO2 by volume with 0.83 gal
of glass bubbles iM16K would only cost
about $8.76 for 100 gallons.
C
0,4
On a volume basis, glass bubbles
are cheaper than TiO2.
0,3
This difference is about $47/100 gallons
of paint or $0.47/gallon as shown.
0,2
0,1
0
0
5
10
15
20
25
wt% TiO2 replaced
52
3M Confidential.
© 2013
3M. 3M.
All Rights
Reserved
© 2014
All Rights
Reserved.
Cost Exercise: Finished raw paint material
Raw Material Cost $
Raw materials cost/gallon of paint vs. TiO2 replacement
with 3M™ Glass Bubbles iM16K
13,9
13,7
13,5
13,3
13,1
12,9
12,7
12,5
12,3
12,1
11,9
A
Basis: 100% Acrylic paint
(Formula B) with 5 vol%
ceramic microspheres W-410
B
C D
0
5
10
15
20
25
wt% TiO2 Replaced
53
3M Confidential.
© 2014
3M.3M.
AllAllRights
Reserved.
© 2013
Rights Reserved
Test Data
System
Formula
Opacity
N=16, SD=.1-.4
60° Gloss
85° Gloss
Scrub
N=4, SD=30-40
No glass bubbles
A
96.18
3.5
3.03
1079
Replace 5% TiO2 with
B
96.34
3.77
3.1
960
Replace 15% TiO2 with
C
96.01
3.6
2.77
1011
Replace 15% TiO2 with other fillers
(no glass bubbles)
D
95.55
3.43
2.92
976
All formulations contain 5 vol% 3M™ Ceramic Microspheres W-410
54
3M Confidential.
© 2014
3M.3M.
AllAllRights
Reserved.
© 2013
Rights Reserved
Summary: statistically significant improvement in opacity & scrub resistance
96,7
1100
96,5
950
95,9
900
95,7
850
Opacity(Mean)
Scrub
A
B
3M Confidential.
D
A = 5% W410
B = -5%TiO2 with iM16K
C = -15% TiO2 with iM16K
D = -15% TiO2 with other
fillers/no glass bubbles
800
Paint Formulation
55
C
Scrub Cycles
Opacity
1000
96,1
95,3
 Scrub resistance maintained
≈ Drop in opacity controlled
 Cost reduced compared to Formula A
1050
96,3
95,5
3M™ Glass Bubbles iM16K and
3M™ Ceramic Microspheres
Samples A-D all have 5 vol%
ceramic microspheres W-410
© 2014
3M.3M.
AllAllRights
Reserved.
© 2013
Rights Reserved
Cost Formulation Strategies
 3M™ Glass Bubbles and 3M™ Ceramic Microspheres can
offer the formulator alternatives to optimizing cost while
maintaining or improving opacity and durability properties
such as scrub resistance.
 Further formulation optimizations should be tested to
enhance desired properties.
56
3M Confidential.
© 2014
3M.3M.
AllAllRights
Reserved.
© 2013
Rights Reserved
Ceramics and Glass Bubbles in
Industrial Latex Paint
57
Coating: White Acrylic Latex
3M™ Ceramic Microspheres White Grade W-410
3M™ Ceramic Microspheres White Grade W-610
Other products evaluated:
Conventional Calcium Carbonate
Conventional Synthetic Silica Matting Agent
Commercially purchased solvent based alkyd paint
58
Example Formulation
MATERIAL
VOLUME %
DI Water
11-12
Dispersant
1.6-1.7
Wetting Agent
.2
Defoamer
0.04
Ph Adjuster
0.7-0.8
TiO2(White Pigment)
6-6.5
Ceramic Microspheres (W-410 or W-610), calcium carbonate, or
silica matting agent
0 or 4.5-5.0
Letdown: Acrylic resin
63-69
Coalescing solvent 1
5.6-6.1
Coalescing Solvent 2
1.8-2
Flash rust Inhibitor
0.1
iM16K or iM30K glass bubble(s)
0 or 4.5-5.0
Rheology Modifier
0.6-0.7
Total
100%
PVC=27, Volume solids 41-43, VOC’s approx 1.3 lbs/gal
59
One of ceramic microspheres, calcium carbonate, glass bubbles, or silica matting agent was used.
Tests with Data Reported
Additional Tests*
Gloss 60° ASTM D523
Adhesion- ASTM D3359
Dry Film Thickness- ASTM D7091
Pencil Hardness(Gardco Wolff) ASTM D3363
Opacity
SAG resistance ASTM D4400
QUV-1000 hrs- ASTM D4329
Heat resistance(11 hrs at 200F)
Salt Spray 1000 hrs-ASTM B117
Environmental Cycling(65C/95%) 672hrs
Taber Abrasion resistance-ASTM D4060
Water Immersion ASTM D870
Washability- ASTM D3450
Grind
Color
Substrates:
3003 aluminum Q-panel(DFT 1.3-1.6 mils) and 1.5-2.3 for taber
Leneta 3B Opacity charts for sag, opacity, color, 10 mil panels for
washability
pH
Settling- Can Stability
Viscosity
Theoretical % NV- wt, Vol, PVC
Dry Time- ASTM D1640
Graffiti resistance
* No significant differences between formulations observed with exception of dry time which was longer for alkyd.
60
Taber Abrasion Wear Cycles per mil coating thickness-ASTM D4060
W=Wear cycles per mil Average
Higher number of
cycles equals better
wear resistance
800
750
700
650
600
550
500
450
400
350
300
61
5% calcium carbonate
5% Conventional Silica
flattener
5% W-410
5% W-610
5% iM30K only
5%iM16K only
Alkyd
Salt Spray 1000 hrs-ASTM B117
3003 Aluminum
3,5
3
SALT SPRAY
ASTM B-117
Scribed
Blistering
after 96 hrs.
2,5
Salt Spray 96 Hours Rank on
aluminum(3= Best)
2
Salt Spray 1000 Hours Rank on
aluminum(3= Best)
1,5
1
No Observable
Corrosion after 1000
hrs for all samples
0,5
0
5% W-410
62
5% W-610
5% calcium
carbonate
5% iM30K only
5%iM16K only
5% Conventional
Silica flattener
Alkyd
1000 Hours Salt Spray
(5% W-410 Loading)
63
60° Gloss Readings
60 gloss aluminum Average of 3
30
25
20
15
60 gloss aluminum Average of 3
10
5
0
5% calcium carbonate 5% Conventional Silica
64
5% W-410
5% W-610
5% iM30K
5%iM16K
Alkyd
QUV 1000 Hours 60° Gloss Retention
60 °gloss change (%) After 1000 Hours QUV "A"
90
80
70
60
50
% 60 °gloss drop
40
30
20
10
0
5% calcium carbonate
65
5% W-410
5% iM30K only
5%iM16K only
Alkyd
Washability Test
Reflectance Recovery After washability with Leneta Black Stain 50 cycles ASTM D3450
100=Best
100
99
98
97
96
95
94
93
92
91
5% calcium carbonate 5% Conventional Silica
66
5% W-410
5% W-610
5% iM30K only
5%iM16K only
Alkyd
Cumulative Ranking Chart
Opacity
Corrosion
Resistance
Abrasion
Resistance
Matting
Efficiency
Washability
Leneta stain
QUV-Gloss &
Color
Retention
=
=
=
=
=
=
=
- -
=/+
+
-
N/A
5% W-410
=
=
++
=
=
+
5% W-610
=
=
++
=
=
N/A
5% iM30K
++
- - -
++
+
- - -
+
5%iM16K
+
- - -
++
+
++
+
Commercially
purchased
solvent based
alkyd
+
-
- -
N/A
=
=
System
designation
5% calcium
carbonate
5% Conventional
Silica
67
Part 4: Solar reflectivity with
Glass Bubbles
68
On the outside of a structure, solar radiation dominates. To prevent the heating of a
surface by the sun, the first step is to reflect as much of the solar radiation as possible.
Thus the first goal is to have the visible and near and IR wavelengths reflected as
completely as possible (0.28 to 2.5 μm ). The solar radiation that is not reflected is
absorbed by the surface. At that point, the absorbed energy is in the form of heat near
room temperature. (That heat can either conductively transfer into the structure, or it
can be re-emitted to the atmosphere.
Since the heat is now at near-room temperature, we need a high thermal wavelength
(2.5to 40 μm ) emissivity to effectively re-emit as much as possible back to the
atmosphere.
In summary, for an exterior surface, the goal is high solar wavelength reflectivity and
high thermal wavelength emissivity.
69
Solar Irradiance
1.6
UV
5%
Visible
46%
N-IR
49%
Solar Irradiance (W/m².nm)
1.4
1.2
1
0.8
0.6
0.4
0.2
0
300
400
500
600
700
800
900
1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 2100 2200 2300 2400 2500
Wavelength (nm)
70
Solar paint STD formulation
(with CaCO3)
raw material
Water
Wetting agent
TiO2
CaCO3
Acrylic dispersion
Thickener
Anti-foam
Totals
Density(g/cc)
1.00
1.16
4.10
2.70
1.06
1.06
1.00
1.58
Weight
69.57
0.80
61.50
121.50
94.68
2.47
0.29
350.81
Solids by weight %
Solids by volume %
Density wet
Density dry
71
W %
19.83
0.23
17.53
34.63
26.99
0.70
0.08
100.00
65.17%
45.00%
1.58
2.29
Volume
69.57
0.69
15.00
45.00
89.32
2.33
0.29
222.20
Filler Vol =
Binder Vol=
PVC =
CPVC =
CPVC/PVC =
V%
31.31
0.31
6.75
20.25
40.20
1.05
0.13
100.00
Vol Dry
0
0.21
15.00
45.00
39.14
0.60
0.05
100.00
% Vol Dry
0
0.21
15.00
45.00
39.14
0.60
0.05
100.00
60.00
40.00
60.00
62.23
1.04
Solar paint S22 formulation
raw material
Water
Wetting agent
TiO2
CaCO3
Acrylic dispersion
3M Glass Bubbles S22
Thickener
Anti-foam
Totals
Density(g/cc)
1.00
1.16
4.10
2.70
1.06
0.22
1.06
1.00
1.08
Weight
69.57
0.80
61.50
0.00
94.68
9.90
2.47
0.29
239.21
Solids by weight %
Solids by volume %
Density wet
Density dry
72
W%
29.08
0.33
25.71
0.00
39.58
4.14
1.03
0.12
100.00
48.92%
45.00%
1.08
1.17
Volume
69.57
0.69
15.00
0.00
89.32
45.00
2.33
0.29
222.20
Filler Vol =
Binder Vol=
PVC =
CPVC =
CPVC/PVC =
V%
31.31
0.31
6.75
0.00
40.20
20.25
1.05
0.13
100.00
Vol Dry
0.00
0.21
15.00
0.00
39.14
45.00
0.60
0.05
100.00
% Vol Dry
0.00
0.21
15.00
0.00
39.14
45.00
0.60
0.05
100.00
60.00
40.00
60.00
67.52
1.13
Testing Equipment:
Spectrophotometer Cary 500
UV – Visible - N-IR
+ Integrated Sphere
Labsphere Integrated Sphere
Measurement: Hemispherical Reflectance properties
73
Solar reflectance, white paint
100
90
80
% Reflectance
70
60
50
40
Sample
White STD
White S22
TSR
81.76
86.18
UV
12.36
13.24
Vis
89.48
92.31
IR
81.13
87.39
30
20
10
0
250
750
1250
1750
2250
Wavelength (nm)
White STD
74
White S22
Osram Ultra-Vitalux lamp
Painted aluminum panel
Thermocouple
Data logger
75
Back side temperature versus Time
100
90
45% CaCO3
45% S22
Temperature (°C)
80
Average temperature
reduction = 3.25°C
70
60
50
40
30
0
76
10
20
30
Time (minutes)
40
50
60
Potential Applications
 Roof coatings, wall paint
 Mobile-Home, Caravans
 Refrigerated Storage Warehouses
 Refrigerated trucks
 Oil & Gas outdoor storage tanks
 Cryogenic tanks and tankers
 Gel coats for pleasure boat cabins
 Etc….
77
3M™ Glass Bubbles
Application in Paint – Anti-Condensation
78
Test Method Development - Condensation
Test method development:
“Condensation Time”
79
Peltier cooling
system
Aluminum painted
panel
“Cold” Box
Heating/ventilation System
80
Saturated water solution of
ammonium
dihydrogenophosphate
First drop of condensation
81
Test Method Settings
 Fish tank:
― Temperature = 22°C
― Dew point = 19 – 20 °C
 Cool box:
― Temerature = 3°C
 Measure of the first drop of condensation to fall down
82
Evaluation of Existing Anti-condensation Paints
Paint Density (g/cc)
Density dry film (g/cc)
Reference paint:
"anti"anti"anti"anti"antistandard wall & condensation" condensation" condensation" condensation" condensation"
ceiling
#1
#2
#3
#4
#5
1.49
1.11
1.04
0.98
0.97
0.90
2.42
1.21
1.08
0.95
0.94
0.79
W% Solids
56.0%
58.0%
54.0%
37.0%
52.0%
43.0%
Volume % Solids
34.4%
53.4%
52.2%
38.3%
53.4%
48.7%
24
20
26
29
41
44
Avg condensation time (min)
83
Comparison Dry Film Density vs Performance
50
3.00
45
2.50
Density Dry Film (g/cc)
Condensation Time (mn)
40
35
2.00
30
25
1.50
20
1.00
15
10
0.50
5
0
0.00
Reference paint:
"anti-condensation" # 1"anti-condensation" # 2"anti-condensation" # 3"anti-condensation" # 4"anti-condensation" # 5
standard wall & ceiling
Avg condensation time (min)
84
Density dry film (g/cc)
Development of an optimized anti-condensation paint starting formula
 Selection of a base formula
 Mixture Design
― % binder, CaCO3 and Glass Bubbles
― Linear Regression
― Paint Formula Model
― Optimized Formula
85
Development of an optimized anti-condensation paint starting formula
Raw Material
Water
Dispersant
TiO2
CaCO3
Styrene-Acrylic dispersion
Preservative
Glass Bubbles S22
Thickener 1
Thickener 2
Anti-foam
Totals
Weight % Solids
Volume % Solids
Wet Density
Dry Density
Condensation time
86
Weight
52.44
0.80
41.00
0.00
77.28
0.39
11.00
2.21
9.45
0.29
194.87
Weight %
26.91
0.41
21.04
0.00
39.66
0.20
5.64
1.13
4.85
0.15
100.00
48.7%
50.0%
0.97
0.95
45 mn
Volume
Volume %
52.44
26.22
0.69
0.35
10.00
5.00
0.00
0.00
75.03
37.52
0.35
0.18
50.00
25.00
2.11
1.05
9.09
4.55
0.29
0.15
200.00
100.00
Dry Volume
Volume pigment
Volume Binder
PVC
CPVC
CPVC/PVC
0.21
10.00
0.00
36.39
0.35
50.00
1.00
2.00
0.05
100.00
% Dry Volume
0.00
0.21
10.00
0.00
36.39
0.35
50.00
1.00
2.00
0.05
100.00
60.00
40.00
60.0%
69.5%
1.16
Conclusions
Large performance variability among tested anti-condensation paints
 Some “anti-condensation” paints do not perform at all
 How does it work ?
― Increased Surface Temperature of Paint:
87
•
Low Thermal Conductivity
•
Temperature Increase

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