Dragonite™ Halloysite Clay and AMIRON
Advanced Natural Iron Oxide:
Minerals for Non Halogenated Flame
Retardancy and Smoke Suppression
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. 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
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
Member Company of
3
Technology Description - What is Halloysite?
100 nm
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
4
Dragonite Chemistry
External siloxane surface (Si-O-Si)
Scroll-like
silica outer
shell
Alumina-like
inner lumen.
(Amphoteric)
0.75 nm
Internal aluminol surface (Al-OH)
Inner surface OH
Inner OH
O atom
Al atom
Si atom
H2O molecule
Structurally
bound water
trapped
between each
layer
5
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
Bulk Density
BHT Pore Volume
2.53
~16 lbs/ft3
20%
Oil (linseed) Absorption
40 lbs/ 100 lbs
Cation Exchange Capacity
11 meq/100g
6
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
Typical Analysis of Dragonite HP Halloysite Product
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
95.5
-1.64
4
68.4
90.5
89.5
80.93
WI CIE YI DIN 6167
61
7
Moisture
%
1.4
8
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
Dragonite Thermal Stability by TGA
100
1.0%
Weight (%)
98
96
94
92
Total Water
Release~15%
90
88
86
84
100
200
300
400
500
600
700
Temperature (°C)
10
Ceramification? Dragonite™ HP & Glass Fiber
11
Case Study 1:
Encapsulation of RDP into Dragonite HP for HDPE
Pallet– 25% (HNT-RDP) vs. Untreated HNT
Property Unit Control HDPE HNT 25% (RDP-HNT) 25% 374.5Cel
100.4%
100.0
90.0
gm/cc 0.944 1.112 1.09 80.0
Flex Modulus Kpsi 108 222 134 70.0
Flex Strength psi 2880 4300 2917 60.0
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 TG %
Density NOVA HDPE CTRl
RPD-30-25
50.0
HDPE-25%Untreated
40.0
30.0
20.0
10.0
0.0
100.0
200.0
300.0
400.0
Temp Cel
500.0
600.0
700.0
800.0
4 mil compressed HDPE film with 25 % (RDP-HNT)
6 mil HDPE film with 25% HNT
12
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
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
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
RDP – 33% Free vs. Vacuum-loaded in HNT
100.0
80.0
TG %
70.0
60.0
50.0
3
Density g/cm³
90.0
Halloysite Filled Tubes
Halloysite Empty Tubes
(RDP+30%HNT) VAC/ 345 C
2
RDP+30% HNT /346 C
1
40.0
30.0
RDP Td =401.8 C
0
0
10
20
30
40
50
60
70
80
90
100
WEIGHT % Halloysite
20.0
100.0
200.0
300.0
400.0
Temp Cel
500.0
600.0
700.0
16
4:1 PC/ABS + Halloysite + 9% free RDP (TSE mixed) Control
2
3
90.70
0.3
0
0
9
0
1.183
85.70
0.3
5
1
8
0
1.202
83.70
0.3
7
1.4
7.6
0
1.218
PC/ABS
PTFE
Dragonite Halloysite
RDP added with feed (barrel-1)
RDP added with pump (barrel-5)
Ricon 184 SBD
Specific Gravity
0
0
1.168
MFR, 260 C, 2160 gm, 5 min preheat, g/10'
Flex modulus,1 %, kpsi
Flex Strength, psi
6.2
376
13125
20
391
20
447
15048
20
476
14954
9051
47
11.8/PB
NB
V2
Yes
8700
45
2.1/CB
NB
V0
9702
17
1.74/CB
NB
V0
No
9367
10.2
1.40/CB
NB
V0
No
<10
S/E
<20
S/E
91,93
94,94
Tensile Strength, psi
% El @ break
Notched Izod Impact, ft-lb/in
Unnotched Izod Impact ft-lb/inch
UL 94 VB 1/16" samples, 5 X5 X2
Flaming VB Drip, burning cotton
100
0
0
Bayblend
3016
5 flames, 5 sec each,UL 94 Vertical , total burn time
Burning rate horizontal, seconds/mm
>30 s
S/E
HDT, 264 psi, 2 C/ minute ramp
123 C
83
17
4:1 PC/ABS + Encapsulated Dragonite
(33%RDP-67%HNT) 0.3% PTFE
Control
Bayblend
3016
1
2
3
4
5/ Free
RDP
1.75
3.5 0.3 1.182 3.5 7 0.3 1.212 5.25 10.5 0.3 1.235 7 14 0.3 1.253 5.5 5 1 1.204 %RDP % Dragonite Halloysite % PTFE Specific Gravity MFR, 260 C, 2160 gm, 5 min preheat,
g/10' Flex modulus,1 %, kpsi Flex Strength, psi Tensile Strength, psi % El @ break Notched Izod Impact, ft-lb/in UL vertical, 23x 10 sec S/E, 1/16” 5 flames, 5 sec each,UL 94 Vertical ,
total burn time S/E burning rate horizontal, seconds/mm Solid residue, 600 C 0 0 0.3 1.165 9 0 0.3 1.183 6.4 380 13369 8809 28 9.7/PB V2 20 391 >30s NO S/E 13.7 NA YES S/E >30 s Yes S/E 17.9 <20 S Yes S/E 22.2 <12 s Yes S/E 22 < 8 s Yes S/E 20 NA YES S/E HDT, 264 psi, 2 C/ minute ramp 122 83 117 112.5 107 102 103 8700 45 2.1/NB VO 7.8 7.4 8.1 9.2 420 462 514 477 14328 14997 15440 14952 8992 9257 9231 9397 15 10 8.9 7.8 3.2/HB 1.62/CB 1.37/CB 1.44/CB V1 V0 V0 V0 12 468 15393 9540 7.7 2.32/CB V0 18
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
CASE STUDY –III
Replacement of ATO by Dragonite HP in Hal- FR
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
20
ATO Replacement by Dragonite HP in f-PVC
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% ATO
1.336
V0
31.5
3.8%ATO
3.8% Dragonite HP
1.327
V0
32.5
1.9% ATO/
5.7% DragoniteHP
1.32
V0
32
21
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
13
7.6%ATO
54
99
232
9
3510
555
50% ATO 11
replaced
58
93
230
7
3480
627
75% ATO 13
Replaced
61
97
242
7
3760
653
22
Heat Release Rate – ATO Replacement
23
ATO Replacement in Halogenated FR-PP
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) HNT YG 59290 Speific Gravity 12.5 1.08 6.25 6.25 1.11 3.12 9.37 1.12 Flex modulus, tangent, Kpsi Flex Strength, psi Tensile Strength, psi % el @ yield % El @ break 245 6196 4040 6.1 22 286 6353 3718 4.2 25 289 6433 3876 4.2 8 0.43/8.13 13.86 VVV No Yes 0.49/6.7 13.62 VVV No Yes 0.46/4.62 10.8 VX No No < 5 sec <5 sec 32 Horizontal burn , stopped after sec. Sag during burning UL 94 rating SE No V0 SE No VO SE Yes V2 Horizontal rate of burning LOI SE NA SE 24.5 SE NA Notched Izod / Unnotched Impact, ft-lb/in MFR, 230 C, 2160 UL vertical, 3x 10 sec cont. flaming drip S/E < 30 seconds Total Time before extinguish,sec 24
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
CASE STUDY –IV FR-Polypropylene Homopolymer
Dragonite vs. Magnesium Hydroxide (MDH)
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
AMIRON Natural Goethite – Yellow Iron Oxide Hydroxide (Fe+++OOH) Iron Oxide Resource
Measured Resource
3,302,275 tons
27
Goethite as SS and Char Builder in CPVC
% 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 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
28
Role of FeOOH in FR/ SS of ABS
•  FeOOH+HCL àFeOCl
+H2O
LOI Ds,
% / gm % Char Yield ABS 18 113 10.7 ABS/CPVC/
FeOOH (80/16/4 ) 31 64 23 •  FeOCl +2HCl à
FeCl3+2H2O
•  FeOCl and FeCl3 both
Lewis Acid – char formers
Ref: Peter Carty, Poly. Degradation
and Stability, 75 (2002) 173-178
29
FeOOH as Smoke Suppressant and Char
Builder in f-CPVC
40
Dmax %/gm
35
% LOI
Dmax /g
Char %
30
None
30.6
36
20.8
25
ATO
35.8
50
20.4
20
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
15
10
5
0
0
2
4
% FeOOH
6
8
30
Conclusions
DRAGONITE is an environmentally safe and easy to disperse versatile additive which improves FR
both in condensed and vapor phase via multiple mechanisms.
DRAGONITE is very good synergist with existing halogenated and non-halogenated FR additives.
In PC/ABS, DRAGONITE reduces the required amount of phosphate FR additive to achieve V0 at
1/16”. As little as 5% DRAGONITE 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, DRAGONITE can replace as much as 50% of ATO without affecting FR
performance while lowering smoke density and improving mechanical properties.
DRAGONITE 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.
AMIRON Goethite hydoxylated iron oxide is an effective smoke suppressant and char builder for
both halogenated polymers or non-halogenated polymers (ABS, PMMA) modified with
halogenated FR.
31
Thank You For Your Time
Q&A