DRAGONITE ™ New Developments using Halloysite for Reinforcement, Fire Retardancy and Foams AMI – Minerals in Compounding 2012 Atlanta November 27 th -28 th Dr. Chris DeArmitt - CTO The statements herein are believed to be accurate and reliable, but are presented without guarantee, warranty or responsibility of any kind, expressed or implied, including that any such use is free of patent infringement.
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DRAGONITE™
New Developments using Halloysite for
Reinforcement, Fire Retardancy and Foams
AMI – Minerals in Compounding 2012
Atlanta November 27th-28th
Dr. Chris DeArmitt - CTO
The statements herein are believed to be accurate and reliable, but are presented without guarantee, warranty or responsibility of any kind, expressed or
implied, including that any such use is free of patent infringement.
Agenda
Applied Minerals
Halloysite structure & properties
Enhancing plastics
Case study: Cycle time reduction
Case study: Injection molded foam
Case study: Extruded foam
Case study: FR HDPE pallets
Commercial aspects
Conclusions
2
Applied Minerals at a Glance
US based publicly traded SEC reporting company
Owner and operator of the Dragon Mine Halloysite Clay Deposit in Utah USA
Over 30 years of proven reserves
Product grades marketed under the Dragonite™ trade name
World renowned technical experts in geology, minerals characterization,
plastics and materials
Over $ 7M invested to date in resource characterization and quantification
Became commercial in 2010 with 30 000 tons annual capacity and expanding
significantly in 2012
3
Characterization and Quality Control
4
Length 0.2-2 μm
Outside Diameter 50-70 nm
Inside Diameter 15-45 nm
Aspect Ratio (L/D) 10-40
Particle Size (d100) < 5 μm 95-100%
Particle Size (d90) < 2 μm 80-98%
BHT Surface Area 65 m2g-1
True Specific Gravity 2.53 gcm-3
Bulk Density ~16 lbs / ft3
BHT Pore Volume 20%
Oil (linseed) Absorption 40 lbs / 100 lbs
Cation Exchange Capacity 11 meq /100g
1 micron
Dragonite Chemistry
5
External siloxane
surface (-Si-O-Si-)
Internal aluminol
surface (-Al-OH)
H2O molecule
Inner surface OH
O atom
Si atom
Al atom
Inner OH
0.7 nm
Dragonite™ Intrinsic Properties and Applications
High aspect ratio
• Reinforcement of plastics, elastomers, coatings etc.
High surface area
• Catalysts, adsorbents, carrier, elastomers, immobilization, nucleation of
• Fire retardance, temperature indicator, foaming agent
6
Agenda
Applied Minerals
Halloysite structure & properties
Enhancing plastics
Case study: Cycle time reduction
Case study: Injection molded foam
Case study: Extruded foam
Case study: FR HDPE pallets
Commercial aspects
Conclusions
7
Dragonite in Plastics
Plastic
Type
Reinforcement Cycle Time /
Nucleation
Transparent
Film
Flame
Retardance
PE ✔ ✔ ✔ ✔
PP ✔ ✔ ✔ ✔
EVA ✔ TBD ✔ ✔
PA6 ✔ ✔ TBD ✔
PA12 ✔ ✔ TBD ✔
PVC ✔ TBD ✔ ✔
PLA ✔ ✔ ✔ ✔
Epoxy ✔ TBD TBD ✔
EPDM ✔ TBD TBD ✔
Suggested
Grade
Dragonite™
XR or HP
Dragonite™
HP
Dragonite™
HP
Dragonite™
XR
8 Transparent at 10% in PVA and 65% in SBR
Reinforcement without Embrittlement
Isotropic fillers retain impact but do not reinforce
Reinforcing fillers ruin impact resistance and elongation to break
Halloysite reinforces and retains or improves impact and elongation
This is possible due to shape, surface area and easy dispersibility
9
Impact &
elongation
Strength &
modulus
FKM PE, PP PVC, PA12 PET, PA6 Water
10
Very low polarity
~20 mJm-2
Low polarity
~35 mJm-2
Medium polarity
~40 mJm-2
High polarity
~45 mJm-2
Very high polarity
~70 mJm-2
Halloysite has been shown to disperse well in all types of system, from
apolar to very polar
Wetting through the tubes gives mechanical bonding even in cases where no
specific chemical interaction takes place
In thermosets, thermoplastics and elastomers, effective reinforcement is
reported even without dispersants or coupling agents
Dispersants and coupling agents may however be used
Dispersibility of Halloysite and Polarity
10
Halloysite in PA6 – Nucleation Boosts Productivity
11 Mechanical Behaviour and Essential Work of Fracture of Halloysite Nanotubes Filled Polyamide 6
Nanocomposites, K. Prashantha, H. Schmitt, M.F. Lacrampe, P. Krawczak, Composites Science and
Technology 71: 1859-1866 (2011).
He
at F
low
End
o U
p (
mW
)
Temperature (°C) 100 125 150 175 200 225
5
10
15
30
35
40
50
20
25
45 Neat PA 6
PA6 + 2 % HNT
PA6 + 4 % HNT
PA6 + 6 % HNT
Halloysite in PA6 – Dramatically Better Mechanicals
12 Composites of polyamide 6 and silicate nanotubes of the mineral halloysite: Influence of molecular weight on thermal, mechanical and rheological properties
Ulrich A. Handge, Katrin Hedicke-Höchstötter, Volker Altstädt, Polymer, 51: 2690-2699 (2010).
Yo
un
g’s
Mo
du
lus (
MP
a)
Halloysite (weight %) 0 5 10 15 20 25 30
2500
3000
3500
4000
4500
5000
5500
PA6 B27 E Low Mwt
PA6 B40 High Mwt
Halloysite in PA6 – Dramatically Better Mechanicals
13 Composites of polyamide 6 and silicate nanotubes of the mineral halloysite: Influence of molecular weight on thermal, mechanical and rheological properties
Ulrich A. Handge, Katrin Hedicke-Höchstötter, Volker Altstädt, Polymer, 51: 2690-2699 (2010).
Yie
ld S
tre
ss (
MP
a)
Halloysite (weight %) 0 5 10 15 20 25 30
74
76
78
84
88
90
94
PA6 B27 E Low Mwt
PA6 B40 High Mwt
80
82
86
92
FR in PA6
14
The suitability of halloysite nanotubes as a fire retardant for nylon 6
D.C.O. Marneya, L.J. Russell, D.Y. Wu, T. Nguyen, D. Cramm, N. Rigopoulos, N. Wright and M. Greaves
Polymer Degradation and Stability, 93 (10): 1971-1978 (2008).
Time (seconds)
Heat
Rele
ase R
ate
(kW
m-2
) 1400
1200
1000
800
600
400
200
0 800 700 600 500 400 300 200 100 0
PA6 Control THR 200
PA6 +5% Halloysite THR 196
PA6 +10% Halloysite THR 181
PA6 +15% Halloysite THR 175
PA6 +20% Halloysite THR 166
PA6 +30% Halloysite THR 156
Agenda
Applied Minerals
Halloysite structure & properties
Enhancing plastics
Case study: Cycle time reduction
Case study: Injection molded foam
Case study: Extruded foam
Case study: FR HDPE pallets
Commercial aspects
Conclusions
15
Dragonite HP: DSC Results in HDPE
Performed independently by Dr. Yash Khanna
Material Tcc
3ºCmin-1
Tcc
10ºCmin-1
HDPE Control 1 117.3 114.5
HDPE Control 2 117.3 113.9
115.2
114.9
Average 117.3 114.6
+ 1% Dragonite HP 119.6 116.2
+ 1% Dragonite HP 119.5 116.5
Average 119.55 116.35
16 US20120101209A1 Nucleating Agent for Polyethylenes