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Dragonite

Applied Minerals Brand

Products:2
DRAGONITE™ is a versatile Halloysite product grade with a wide range of applications including controlled release, environmental remediation, agriculture, paints and coatings, and catalysts.
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Knowde Brand Summary

Identification

Chemical Family

Features & Benefits

Labeling Claims

Applications & Uses

Knowde Brand Highlights

High Performance Additive for Thermoset Resins

Key Benefits

  1. Reinforcement - Dragonite has a high surface area and aspect ratio to provide substantial improvement in both stiffness and strength.   The   flexural   modulus   of   Dragonite is 130 -150 Gpa.
  2. Impact Enhancer - Unlike other reinforcements, Dragonite allows you to dramatically improve impact resistance. In certain epoxy systems, a 2% Dragonite loading can improve impact resistance by up to 400%.
  3. Electrical Properties - Dragonite in an insulator with a low dielectric constant making it ideal for applications where electrical properties are a key performance objective.
  4. Additional Benefits include CTE Reduction, Increased Flame Retardance, and Improved Dimensional Stability.
  5. 100% Natural Ingredient - Dragonite Halloysite is non-­‐toxic and natural -­‐ demonstrating a high compatibility without posing any risk to the environment.
DRAGONITE in Polyurethane Thermosets

Mechanical Property Improvements

The tensile strength, elongation to break, Young’s modulus, and Shore A Hardness were all improved with the addition of 1.0% halloysite to an MDI polyurethane system.

Neat MPU 10.4  272 15.2 92
0.5% Halloysite 21.7 365 21.4 92
1% Halloysite 22.9 347 21.5 94
5% Halloysite 21.1 278 48.2 97

Gong, B., Ouyang, C., Yuan, Y., & Gao, Q. (2015). Synthesis and properties of a millable polyurethane elastomer with low halloysite nanotube content. RSC Adv., 5(94), 77106–77114.

 

Polyurethane / Halloysite Crosslinked Network

DRAGONITE in Epoxy Thermosets

Fracture Toughness Improvements

The fracture toughness of the halloysite particle modified epoxies was noticeably increased, with the greatest improvement in KIC up to 50% and in GIC up to 127%. The improvements in fracture toughness are mainly attributable to mechanisms such as crack bridging, deflection and plastic deformation of the epoxy around the particle clusters.The fracture toughness of the halloysite particle modified epoxies was noticeably increased, with the greatest improvement in KIC up to 50% and in GIC up to 127%.

The improvements in fracture toughness are mainly attributable to mechanisms such as crack bridging, deflection and plastic deformation of the epoxy around the particle clusters.

Deng, S., Zhang, J., Ye, L., & Wu, J. (2008). Toughening epoxies with halloysite nanotubes. Polymer, 49(23), 5119–5127.

 

CTE and Mechanical in Glassy and Rubbery States Improvement

Halloysite was incorporated in a cyanate ester cured epoxy resin to lower the CTE value and increase the mechanical properties of the epoxy resin.

Sample (wt%) E’ at 50C (Mpa) Increase (%) E’ at 210C (Mpa) Increase (%)
Neat Resin 2701   62.8  
4% Halloysite 3354 24.2 88.1 40.3
8% Halloysite 3491 29.2 109.7 74.7
12% Halloysite 4283 58.6 139.2 121.7

Liu, M., Guo, B., Du, M., Cai, X., & Jia, D. (2007). Properties of halloysite nanotube– epoxy resin hybrids and the interfacial reactions in the systems. Nanotechnology, 18(45), 455703.

 

Impact Strength Improvements

The impact strength of the halloysite particle modified epoxies was noticeably increased 400% without sacrificing other mechanical properties. The underlying toughening mechanisms responsible for the unusual 400% increase in impact strength were investigated and identified as massive micro-­‐cracking, nanotube bridging/pull out/breaking and crack deflection.

Ye, Y., Chen, H., Wu, J., & Ye, L. (2007). High impact strength epoxy nanocomposites with natural nanotubes. Polymer, 48(21), 6426–6433.

 

Flexural Strength and Modulus Improvement

Halloysite was incorporated in a cyanate ester cured epoxy resin to increase the flexural strength and modulus.

Flexural Modulus and Flexural Strength of Epoxy/Halloysite Nanocomposites

Sample (wt%) Flexural Strength (Mpa) Flexural Modulus (Gpa)
Neat Resin 47 3.26
4% HNTs 100 3.65
8% HNTs 107 3.85
12% HNTs 91 3.98

Liu, M., Guo, B., Du, M., Lei, Y., & Jia, D. (2008). Natural inorganic nanotubes reinforced epoxy resin nanocomposites. Journal of Polymer Research, 15(3), 205–212.

DRAGONITE in Vinyl Ester Thermosets

Fracture and Impact Toughness Improvements

The impact strength of the halloysite particle modified epoxies was noticeably increased 400% without sacrificing other mechanical properties. The underlying toughening mechanisms responsible for the unusual 400% increase in impact strength were investigated and  identified as massive  micro-­‐cracking, nanotube bridging/pull out/breaking and crack deflection.

Fracture Properties of VER and VER/ Halloysite Nanocomposites

Sample (wt%) Fracture Toughness (Mpa m1/2) Impact Toughness (kJ/m²)
Neat VER 1.8 1.5
1% Halloysite 2.1 2.9
3% Halloysite 2.4 3.3
5% Halloysite 2.6 4.1

Alhuthali, A., & Low, I. M. (2013). Mechanical and fracture properties of halloysite nanotube reinforced vinyl-­ester nanocomposites. Journal of Applied Polymer Science, 130(3), 1716–1725.

 

SEM Images of VER/ Halloysite Samples

a. VER resin

b. VER/1%HNT loading

c. VER/3% loading d. VER/5%HNT loading

DRAGONITE in Elastomers

The elastomers market is the largest single user of high performance fillers like carbon black and silica ($5 Billion USD annually). High surface area grades are used as these facilitate processing of the elastomers and also raise the mechanical properties.

DRAGONITE, as a high surface area silicate type filler, would be expected to show promise in elastomeric systems and that has indeed been found to be the case.

The advantages of DRAGONITE in elastomers include:

Incorporation into EPDM (at 100 phr)

  • Tensile strength increased by min. 800%
  • 100% modulus increased by almost 300%
  • Elongation to break increased by almost 300%
  • UL-94 flame retardance rating of V0

Morphological, thermal and tensile propertes of halloysite nanotubes filled ethylene propylene diene monomer (EPDM) nanocomposiles, H. Ismail, Pooria Pasbakhsh, M.N. Ahmad Fauzi, A. Abu Bakar, Polymer Testing 27: 841-850 (2008).

Incorporation into Natural Rubber

  • Excellent dispersion leads to good modulus, strength and elongation to break
  • Concluded to be more effective reinforcement than silica
  • Onset of thermal degradation as measured by TGA, improved by 64°
DRAGONITE in Fluoroelastomers

The advantages of DRAGONITE in fluoroelastomers include:

  • Substantial increase in strength and modulus with full retention of elongation to break
  • No shift in glass transition temperature
  • Increase in thermal stability
Material 100% Modulus (MPa) (E'0 - E') Modulus (MPa) Tensile Strength (MPa) Elongation to Break (%)
FKM gum 2.5 7.45 4.5 197
+5 phr Halloysite 3.0 8.50 6.2 217
+10 phr Halloysite 3.4 13.91 6.8 205
+20 phr Halloysite 3.6 15.48 7.3 200
+30 phr Halloysite 2.6 11.97 5.6 254

Tube-like natural halloysite/fluoroellastomer nanocomposites with simultaneous enhanced mechanical, dynamic mechanical and thermal properties, S. Rooj. A. Das, G. Heinrich, European Polymer Journal doi: 10.1016/j.eurpolymj.2011.06.007.

DRAGONITE in Epoxy Resins

The superior performance seen in thermoplastics and elastomers is mirrored in thermoset materials. In epoxy resins, numerous articles have reported excellent results. Halloysite improves modulus and strength as one would expect for a high aspect ratio filler. Just 5 weight % Halloysite improved the interlaminar shear strength (ILSS) by 25% in carbon fiber reinforced Epon Resin 828 cured with MDA. Toughness was significantly improved at the same time.

Property Neat Epoxy 5% Halloysite 10% Halloysite
Flexural Modulus (GPa) 3.05 3.39 (+11%) 3.59 (+18%)
Flexural Strength (MPa) 110 116 (+16%) 120 (+20%)
K1C(MPa.m1/2) 0.90 1.26 (+40%) 1.35 (+50%)
G1C(MPa.m1/2) 228 456 (+100%) 517 (+127%)

K1C - Critical stress intensity factor (energy needed to initiate a crack)
G1C - Critical strain energy release rate (energy needed to grow a crack)
Toughening epoxies with haloysite nanotubes S. Deng, J. Zhang. L Ye, J. Wu. Polymer. 49. 5119-5127 (2008).

In another study, adding just 2.3 weight % Halloysite improved impact resistance by an astonishing 400%. These benefits are of particular interest in the aerospace industry where light, durable carbon fiber reinforced epoxies dominate.

High impact strength epoxy nanocomposites with natural nanotubes Y. Ye, H. Chen, J.Wu,L.Ye, Polymer, 48: 6426-6433 (2007).

DRAGONITE in Rigid PVC

DRAGONITE improves the properties of rigid PVC. Again, true reinforcement is seen as evidenced by an increase in both strength and stiffness. Even more impressive is that no loss in either impact resistance or elongation to break is seen. In fact, the virgin PVC failed in a brittle mode whereas all samples with DRAGONITE added became ductile.

Property PVC 1% Dragonite 2% Dragonite 3% Dragonite
Flex Modulus (kpsi) 459 490 488 521
Flex Yeild Strength (psi) 13084 13771 13834 14010
Elongation to Break (%) 6 10 9 8
Notched Izod (ft-lb/in) 0.9 0.9 0.9 0.9
unnotched Izod (ft-lb/in) 7.3 7.2 10.2 12.5
DRAGONITE in Other Polymers

DRAGONITE has also proven effective in a wide range of other polymers including PET, PBT, Nylon 12 and PEEK.

Environmental/Recyclability

DRAGONITE is a natural material that allows for reduced energy consumption during part production as well as reduced plastics use through thin-walling enabled by the mechanical property improvements.

DRAGONITE is also recyclable. Customers are aware that fillers are often broken down during recycling operations whereby the extruder damages the particles and the mechanical properties fade with each successive recycling operation. A study using multiple successive extruder passes showed that DRAGONITE enables property retention when recycling because the particles are simply too small to be broken down by extrusion.