1. Dragonite™ Halloysite and Goethite:
Minerals for Non Halogenated
Flame Retardancy and Smoke Suppression
Amit Dharia, Ph.D.
Andre Zeitoun, CEO
AMI Fire Retardants in Plastics
Denver CO, June 14th 2013
www.appliedminerals.com
The statements above 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.

2. Agenda
Applied Minerals
Halloysite structure & Properties
Halloysite as FR /SS /Char forming additive
Case Study I: HDPE Pallet
Case Study II: Halloysite in PC/ABS –RDP
Case Study III: Halloysite as ATO Replacement
Case Study IV: Halloysite With ATH/MDH in Olefins
Case Study V: Goethite(FeOOH) as SS/FR in CPVC and ABS
Conclusions
2

3. Applied Minerals at a Glance
US based publicly traded SEC reporting company.
Owner and operator of the Dragon Mine Halloysite Clay/ Iron Oxide 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 2011 with 30 000 tons annual capacity and expanding in
2013.
Member Company of
3

4. Technology Description - What is Halloysite?
Halloysite is a natural aluminosilicate clay with a hollow tubular morphology
Halloysite nanotubes typically have 1D ~50nm width with lengths ranging from 0.5 to 1
microns giving an aspect ratio of 10~20
Naturally exfoliated morphology means easier dispersion
Traditional uses include fine porcelain, functional filler in paints and paper, food extenders,
cracking catalysts and molecular sieves
Natural, Non toxic, biocompatible. FDA approved for food contact
Green Screen Ranking of 3DG according to draft report by Toxservices
100 nm
4

5. Dragonite Chemistry
5
Scroll-like
silica outer
shell
Alumina-like
inner lumen.
(Amphoteric)
Structurally
bound water
trapped
between each
layer
External siloxane surface (Si-O-Si)
Internal aluminol surface (Al-OH)
Inner surface OH
O atom
Si atom H2O molecule
Al atom
Inner OH
0.75 nm

6. Dragon Mine Halloysite Clay: Typical Analysis
Length 0.5-2 μm
Outside Diameter 50-70 nm
Inside Diameter 15-45 nm
Aspect Ratio (L/D) 10- 20
Particle Size (d100) < 5 μm 95-100%
Particle Size (d90) < 2 μm 80- 98%
BHT Surface Area 65 m2/g
True Specific Gravity 2.53
Bulk Density ~16 lbs/ft3
BHT Pore Volume 20%
Oil (linseed) Absorption 40 lbs/ 100 lbs
Cation Exchange Capacity 11 meq/100g
6

7. Dragonite ™ Halloysite Property Overview
Aluminosilicate mineral: Al2Si2O5(OH)4 . nH2O
Molecular weight: 294.19
CAS: 1332-58-7
Density: 2.54 ± 0.03 gcm-3
Refractive index at room temperature: 1.534, dried at 100°C 1.548
Specific heat capacity: 0.92 kJkg-1K-1
Thermal conductivity: 0.092 WK-1m-1
Thermal diffusivity: 5.04 x 10-4 cm2 sec-1
CTE: 10.0 ± 1.5 perpendicular to the layer, 6.0 ± 2.0 parallel
pH in water 6.4-7.2 in water (Hammet acidity, Pk depends on % moisture,
and pre-drying drying)
Particle shape: 1-2 microns long, 50nm across, 15nm diameter hole
Modulus of a single tubular particle ~130 GPa
Surface area: 65-100m2g-1
7

8. Typical Analysis of Dragonite HP Halloysite Product
8
Typical Analysis
Surface Area
BET
65 m2g-1
Particle Size Distribution: Sedigraph
<10.0 μ <5.0 μ <2.0 μ <1.0 μ <0.5 μ
98.4% 91.0% 70.3% 58.9% 52.8%
Moisture Loss: TGA
40-130°C 130-230°C 230-400°C 400-850°C Total LOI
1.7% 0.3% 0 13.5% 15.5%
Color: Minolta Spectrophotometry
L* a* b* TAPPI Br. Rx Ry Rz WI CIE YI DIN 6167
Moisture
%
95.5 -1.64 4 68.4 90.5 89.5 80.93 61 7 1.4

9. Dragonite™ - Versatile FR additive
• 15-18% w/w bound water coming off at onset of polymer Td of 400° C.
• Bronsted / Lewis acid surface - Catalytic degradation of polymer at very high temperatures
promotes formation of complex molecules – Low Smoke and Char formation
• Hollow lumen traps and stabilizes free radicals – reduces HRR
• Able to encapsulate migrating FR agents into the tubular structure
• Low thermal diffusivity – thermal barrier
• Potential barrier to Oxygen
• Ceramification /sintering of short fibers and formation of network
• Increase Char density and yield – flaming drip resistance
• Safe, solid, non-abrasive (Mohs hardness of 2), easy to meter and disperse
• Small particle size, high surface area, with no low Mw surface sizing
• Long aspect ratio and fine size means higher strength, stiffness, and HDT/ Vicat
9

10. Dragonite Thermal Stability by TGA
100 200 300 400 500 600
Temperature (°C)
Weight(%)
88
96
100
92
84
1.0%
98
94
90
86
Total Water
Release~15%
700
10

11. Ceramification? Dragonite™ HP & Glass Fiber
11

12. Case Study 1:
Encapsulation of RDP into Dragonite HP for HDPE
Pallet– 25% (HNT-RDP) vs. Untreated HNT
12
Temp Cel
800.0700.0600.0500.0400.0300.0200.0100.0
TG%
100.0
90.0
80.0
70.0
60.0
50.0
40.0
30.0
20.0
10.0
0.0
RPD-30-25
NOVA HDPE CTRl
HDPE-25%Untrea
374.5Cel
100.4%
6 mil HDPE film with 25% HNT
4 mil compressed HDPE film with 25 % (RDP-HNT)
Property Unit
Control
HDPE
HNT
25%
(RDP-HNT)
25%
Density gm/cc 0.944 1.112 1.09
Flex Modulus Kpsi 108 222 134
Flex Strength psi 2880 4300 2917
Notched Izod ft-lb/inch 2.1 0.8 1.8
Unnotched Izod ft-lb/inch NB 10 NB
Tensile Strength psi 3256 3600 2845
% El @ break % 38 27 55
Horizontal burn in/minute 0.99 0.85 0.8
Dripping Yes No No
Con.t Drip No Drip No Drip

13. Advantages of (RDP-HNT) & HNT in FR HDPE
Non-halogenated, Good dispersion assisted by RDP encapsulated into HNT
Higher stiffness and strength for both formulations vs. control
Equivalent impact strength as control HDPE using HNT/RDP
Better process ability and production rate
Lower overall density vs. other options
Better Thermal stability (Higher Td, onset in TGA)
Lower than 1 “ / minute burn rate – Barometer to Pass UL 2335
No wax-like continuous flaming drip
Results not possible to achieve using equivalent % w/w MDH or ATH
13

14. Case Study II: Non-HAL FR - PC/ ABS Blend
Commercially very significant blend – Large volume used in cost-critical durable
applications - automotive, appliances, and computer housing.
PC-ABS blends have poor FR properties (LOI 18, Dmax -113 %/gm). Growing demand for
Non-Hal FR-ABS with higher stiffness, strength, higher application temperature (HDT @
264 psi).
Current commercial FR-PC-ABS with 9-15% liquids Phosphates (RDP,BDP, TPP) results
in lower HDT (83 C). FR-PC-ABS blends with similar or better mechanical properties,
Processability but HDT of 100 C or higher at similar cost is desired.
High viscosity liquid phosphates are difficult to meter, and plasticizes the matrix. Migration,
“juicing” of mold results in loss of productivity.
14

15. FR- PC- ABS – RDP
Options for Formulating
o Reduce the amount of total RDP – Partial replacement by Dragonite
o Reduce the amount of free RDP –Encapsulation of RDP in Dragonite
o Optimize Dragonite to RDP ratio
o Add impact modifier to adjust impact strength
o (SMA, SBD,SMA-g-PBD, PS-g-MAH)
15

16. RDP – 33% Free vs. Vacuum-loaded in HNT
16
T e m p C e l
7 0 0 .06 0 0 .05 0 0 .04 0 0 .03 0 0 .02 0 0 .01 0 0 .0
TG%
1 0 0 .0
9 0 .0
8 0 .0
7 0 .0
6 0 .0
5 0 .0
4 0 .0
3 0 .0
2 0 .0
R D P T d = 4 0 1 .8 C
R D P + 3 0 % H N T /3 4 6 C
(R D P + 3 0 % H N T ) V A C /
0
1
2
3
0 10 20 30 40 50 60 70 80 90 100
Halloysite Filled Tubes
Halloysite Empty Tubes
WEIGHT % Halloysite
Densityg/cm³

17. 4:1 PC/ABS + Halloysite + 9% free RDP
(TSE mixed)
17
Control
Bayblend
3016
2 3
PC/ABS 100 90.70 85.70 83.70
PTFE 0 0.3 0.3 0.3
Dragonite Halloysite 0 0 5 7
RDP added with feed (barrel-1) 0 1 1.4
RDP added with pump (barrel-5) 0 9 8 7.6
Ricon 184 SBD 0 0 0 0
Specific Gravity 1.168 1.183 1.202 1.218
MFR, 260 C, 2160 gm, 5 min preheat, g/10' 6.2 20 20 20
Flex modulus,1 %, kpsi 376 391 447 476
Flex Strength, psi 13125 15048 14954
Tensile Strength, psi 9051 8700 9702 9367
% El @ break 47 45 17 10.2
Notched Izod Impact, ft-lb/in 11.8/PB 2.1/CB 1.74/CB 1.40/CB
Unnotched Izod Impact ft-lb/inch NB NB NB NB
UL 94 VB 1/16" samples, 5 X5 X2 V2 V0 V0 V0
Flaming VB Drip, burning cotton Yes No No
5 flames, 5 sec each,UL 94 Vertical , total burn time >30 s <10 <20
Burning rate horizontal, seconds/mm S/E S/E S/E
HDT, 264 psi, 2 C/ minute ramp 123 C 83 91,93 94,94

18. 4:1 PC/ABS + Encapsulated Dragonite (33%RDP-
67%HNT) 0.3% PTFE
18
Control
Bayblend
3016
1 2 3 4
5/ Free
RDP
%RDP 0 9 1.75 3.5 5.25 7 5.5
% Dragonite Halloysite 0 0 3.5 7 10.5 14 5
% PTFE 0.3 0.3 0.3 0.3 0.3 0.3 1
Specific Gravity 1.165 1.183 1.182 1.212 1.235 1.253 1.204
MFR, 260 C, 2160 gm, 5 min preheat,
g/10' 6.4 20 7.8 7.4 8.1 9.2 12
Flex modulus,1 %, kpsi 380 391 420 462 514 477 468
Flex Strength, psi 13369 14328 14997 15440 14952 15393
Tensile Strength, psi 8809 8700 8992 9257 9231 9397 9540
% El @ break 28 45 15 10 8.9 7.8 7.7
Notched Izod Impact, ft-lb/in 9.7/PB 2.1/NB 3.2/HB 1.62/CB 1.37/CB 1.44/CB 2.32/CB
UL vertical, 23x 10 sec S/E, 1/16” V2 VO V1 V0 V0 V0 V0
5 flames, 5 sec each,UL 94 Vertical ,
total burn time >30s NA >30 s <20 S <12 s < 8 s NA
S/E NO YES Yes Yes Yes Yes YES
burning rate horizontal, seconds/mm S/E S/E S/E S/E S/E S/E S/E
Solid residue, 600 C 13.7 17.9 22.2 22 20
HDT, 264 psi, 2 C/ minute ramp 122 83 117 112.5 107 102 103

19. Conclusions – FR PC-ABS
UL V0 rating at 1/16” thickness with partial substitution of RDP encapsulated in
Dragonite
HDT (264 psi) of 100 C or higher achieved with incorporation of Dragonite
Melt Flow– Similar melt flow achieved as RDP alone
Strength and stiffness higher than commercial FR- ABS/PC blend
Need to address impact strength and toughness
19

20. CASE STUDY –III
Replacement of ATO by Dragonite HP in Hal- FR
20
Property`
ATO 1
Premium
ATO2
Standard
Dragonite
HP
50 : 50
HP:ATO1
50 : 50
HP:ATO2
Lead (%) 0.09 0.2 <0.000001 0.045 0.1
Arsenic (%) 0.1 0.25 0.0004 0.05 0.125
Cost (%) 100 80 50 75 65
Dragonite HP other trace elements

21. ATO Replacement by Dragonite HP in f-PVC
21
Formulation: 100 PVC, 46 DOP, 18.4 ATH, 0.15 Stearic acid
0.25 Wax, 3.5 CA/ZN Stabilizer, 1.2 ESO, 7.6 ATO + Dragonite HP)
Sample Specific
Gravity
UL-94
VB Test (1/8”)
LOI
%
PVC Ctrl
7.6 phr ATO
1.336 V0 31.5
3.8 phr ATO
3.8 phr Dragonite HP
1.327 V0 32.5
1.9 phr ATO/
5.7 phr Dragonite HP
1.32 V0 32

22. Cone Calorimeter Results (50 kW/m2) Heat Flux
Sample
Ti
(sec)
Total
Heat
MJ/m2
HRR
KW/m2
Peak
HRR
kW/m2
Mass
Loss
Rate
(g/s.m2
)
Total
Smoke
Flame
Out
time
(sec)
Ctrl
7.6%ATO
13 54 99 232 9 3510 555
50% ATO
replaced
11 58 93 230 7 3480 627
75% ATO
Replaced
13 61 97 242 7 3760 653
22

23. Heat Release Rate – ATO Replacement
23

24. ATO Replacement in Halogenated FR-PP
24
62.5% 12 MFR Profax 6301 PP Flakes, 25% Dechlorane Plus, 0..25% Anox 20 (Mixed using 40:1 L/D 25
mm ZSE)
Antimony trioxide (ATO) 12.5 6.25 3.12
HNT YG 59290 6.25 9.37
Speific Gravity 1.08 1.11 1.12
Flex modulus, tangent, Kpsi 245 286 289
Flex Strength, psi 6196 6353 6433
Tensile Strength, psi 4040 3718 3876
% el @ yield 6.1 4.2 4.2
% El @ break 22 25 8
Notched Izod / Unnotched Impact, ft-lb/in 0.43/8.13 0.49/6.7 0.46/4.62
MFR, 230 C, 2160 13.86 13.62 10.8
UL vertical, 3x 10 sec VVV VVV VX
cont. flaming drip No No No
S/E < 30 seconds Yes Yes No
Total Time before extinguish,sec < 5 sec <5 sec 32
Horizontal burn , stopped after sec. SE SE SE
Sag during burning No No Yes
UL 94 rating V0 VO V2
Horizontal rate of burning SE SE SE
LOI NA 24.5 NA

25. Conclusions – ATO Replacement
Dragonite contains far less lead and Arsenic compared to premium ATO
50% ATO can be replaced by Dragonite HP without affecting FR properties
Better mechanical properties, without loss of Processability, at a similar
density
Significant cost savings
25

26. CASE STUDY –IV FR-Polypropylene Homopolymer
Dragonite-XR vs. MDH- Magnesium Hydroxide
Control 1 2 3 4 5
Dragonite XR 0 0 20 30 40 60
Magnesium Hydroxide (ST) 0 60 40 30 20 0
PP 20 MFI 100 40 40 40 40 40
Flexural Modulus tangent (kpsi) 207 432 467 464 521 557
Flexural Modulus 1% (kpsi) 212 373 391 392 440 461
Flexural Strength (psi) 6517 5131 5350 5347 5666 6200
Tensile Modulus (kpsi) 150 277 275 285 300 294
Tensile Strength (psi) 5180 3242 3182 3189 3650 3818
Notched Izod Impact ft-lb/in 0.44 0.54 0.54 0.5 0.45 0.43
Smoke low low very low very low low
UL 94 Rating V2 V1 V1 V1 V1
26

27. New Development Product: Dragon IOP
Natural Goethite – Yellow Iron Oxide Hydroxide (Fe+++OOH)
27
Iron Resource
Measured Resource 2,104,000 tons
Inferred Resources 688,300 tons
Total resource 2,792,300 tons

28. 28
Typical Analysis of Dragon IOP:
Natural Goethite
Iron Ore Typical Analysis
Mineralogy: Full pattern fitting RIR method (wt.%)
Quartz Hematite Goethite Halloysite Total
.6 17.9 76.5 4.6 100.0
Element Analysis: XRF
SiO2 Al2O3 Fe2O3 CaO MgO Na2O K2O Cr2O3 TiO2 MnO P2O5 SrO BaO LOI Total
4.8 2.0 79.6 0.1 0.1 0.1 0.1 <0.01 <0.01 0.6 0.6 <0.01 <0.01 12.3 100
Trace Elemental Chemistry: ICP-MS
As Cd Co Cr Cu Fe Hg Ni Pb Sr Zn
13.3012 <0.50 45.01 1.72 7.23 197329.9 1.14 18.16 5.40 10.40 165.00

29. Goethite as SS and Char Builder in CPVC
PVC à HCl + Char + Benzene + toluene (Heavy)
CPVC à HCl +Char + Chlorinated Aromatics (Low)
DOP à Pthalic Acid + Cl-C8 Hydrocarbon à Benzene +CO2 (Heavy)
CPVC + FeOOH à HCl+ Char + Highly chlorinated Aromatics (Very low)
DOP +FeOOH à Pthalic Anhydride + Cl –C8 HC +alcohols +alkenes (Low)
Ref: Peter Carty, J. Of Fire Sci., p 483, Vol 17, 1999
29
% CL %DOP Goethite %LOI
Smoke
Density
Char
Yield
Dmax/gm %
PVC 48 0 0 49.6 50 13.7
CPVC 65 0 0 69.4 11 29.3
CPVC 65 30 0 30.6 38 20.8
CPVC 65 30 5 32.6 12 28.9

30. Role of FeOOH in FR/ SS of ABS
• FeOOH+HCL
àFeOCl+H2O
• FeOCl +2HCl à
FeCl3+2H2O
• FeOCl and FeCl3 both
Lewis Acid – char formers
Ref: Peter Carty, Poly. Degradation
and Stability, 75 (2002) 173-178
30
LOI
Ds,
% / gm
% Char Yield
ABS 18 113 10.7
ABS/CPVC/FeOO
H (80/16/4 ) 31 64 23

31. FeOOH as Smoke Suppressant and Char
Builder in f-CPVC
31
0
5
10
15
20
25
30
35
40
0 2 4 6 8
Dmax%/gm
% FeOOH
% LOI Dmax /g Char %
None 30.6 36 20.8
ATO 35.8 50 20.4
AOM 31.7 28 25.1
ZnSnO3 35.8 35 24.2
CHP 32.2 1) 28 26.5
CaO/ZnO 31.6 20 27.7
Fe2O3 32.4 12 28
FeOOH 32.6 12 28.9

32. Conclusions
Halloysite is an environmentally safe and easy to disperse versatile additive which improves FR
both in condensed and vapor phase via multiple mechanisms.
Halloysite is very good synergist with existing halogenated and non-halogenated FR additives.
In PC/ABS it reduces the required amount of phosphate FR additive to achieve V0 at 1/16”. As
little as 5% HNT increases HDT by more than 10° C while improving strength/ stiffness as wells
flame resistance. Properties of suggested blends are better than several commercial grades.
In PVC and non-PVC, Halloysite can replace as much as 50% of ATO without affecting FR
performance while lowering smoke density and improving mechanical properties.
Halloysite is easier to disperse than MDH and can replace as much as 50% of MDH without
affecting mechanical properties while imparting drip resistance (i.e. UL V2 to V1) in olefins.
Goethite hydoxylated iron oxide is one of the best smoke suppressants and char builder for both
halogenated polymers or non-halogenated polymers (ABS, PMMA) modified with halogenated FR.
32

33. Thank You For Your Time
Q&A