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. 

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

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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

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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

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

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

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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

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Typical Analysis of Dragonite HP Halloysite Product

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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

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

100 200 300 400 500 600 Temperature (°C)

Wei

ght (

%)

88

96

100

92

84

1.0%

98

94

90

86

Total Water Release~15%

700

10

Ceramification? Dragonite™ HP & Glass Fiber

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Case Study 1: Encapsulation of RDP into Dragonite HP for HDPE Pallet– 25% (HNT-RDP) vs. Untreated HNT

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Temp Cel800.0700.0600.0500.0400.0300.0200.0100.0

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%Untreated HNT

374.5Cel100.4%

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 

   

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.

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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)

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RDP – 33% Free vs. Vacuum-loaded in HNT

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Temp Cel700.0600.0500.0400.0300.0200.0100.0

TG %

100.0

90.0

80.0

70.0

60.0

50.0

40.0

30.0

20.0

RDP Td =401.8 C

RDP+30% HNT /346 C

(RDP+30%HNT) VAC/ 345 C

0

1

2

3

0 10 20 30 40 50 60 70 80 90 100

Halloysite Filled Tubes

Halloysite Empty Tubes

WEIGHT % Halloysite

Den

sity

g/c

m³

4:1 PC/ABS + Halloysite + 9% free RDP  (TSE mixed) 

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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

4:1 PC/ABS + Encapsulated Dragonite (33%RDP-67%HNT) 0.3% PTFE

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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 

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

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CASE STUDY –III Replacement of ATO by Dragonite HP in Hal- FR

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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

ATO Replacement by Dragonite HP in f-PVC

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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

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

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Heat Release Rate – ATO Replacement

23

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 

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

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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

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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

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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

Goethite as SS and Char Builder in CPVC

PVC HCl + Char + Benzene + toluene (Heavy) CPVC HCl +Char + Chlorinated Aromatics (Low) DOP Pthalic Acid + Cl-C8 Hydrocarbon Benzene +CO2 (Heavy) CPVC + FeOOH HCl+ Char + Highly chlorinated Aromatics (Very low) DOP +FeOOH 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 

Role of FeOOH in FR/ SS of ABS

•  FeOOH+HCL FeOCl+H2O

•  FeOCl +2HCl

FeCl3+2H2O

•  FeOCl and FeCl3 both Lewis Acid – char formers

Ref: Peter Carty, Poly. Degradation

and Stability, 75 (2002) 173-178

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LOI  Ds, % / gm  % Char Yield 

ABS  18  113  10.7 

ABS/CPVC/FeOOH (80/16/4 )  

31  64  23 

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

Dm

ax %

/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

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.

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Thank You For Your Time

Q&A