Sustained Controlled Corrosion Inhibition...•Last 3 years, transitioned from a micro-encapsulation company to a smart pigment manufacturer. •Currently, moving beyond Aerospace

Sustained Controlled

Corrosion Inhibition

Ceramisphere Pty Ltd

10/43 College Street,

Gladesville NSW 2111

Australia

[email protected]

The Bad News

2

No Beer for the next 30 minutes !!

◉ Introduction to Ceramisphere

◉ Micro-encapsulation and coatings

◉ Ceramisphere Encapsulation Technology

◉ Controlled Release Anticorrosion Pigments

◉ Conclusions

3

This document is the property of Ceramisphere Pty Ltd. No part shall be reproduced or transmitted without the express prior written authorisation from Ceramisphere Pty

Ltd, and the contents shall not be disclosed. 3

Outline

◉ Ceramisphere Pty Ltd is manufacturer of controlled release additives for

paints and coatings based in Sydney, Australia.

◉ Our products are based on a patented technology for the encapsulation,

delivery and controlled release of molecules using sub-micron or micron

sized ceramic spheres. Distributed in the USA by Silverfern Chemicals and

by Arya Chem in Canada.

◉ Capabilities:

◉ A fully equipped laboratory facility in Gladesville (Sydney).

◉ NSST chamber and paint booth to perform anti-corrosion evaluations.

◉ Manufacturing plant in the northern suburbs of Sydney.

◉ Highly skilled team composed of chemists, chemical engineers and

materials scientists that is solution oriented and customer focused.

4

Ceramisphere


Ltd, and the contents shall not be disclosed.

Encapsulation and Coatings

A growing business !

5

Figure 1: Development of patents in 5-year intervals (source: database

CAPLUS 17.01.2017; Key words; microcapsules in paints, varnishes and

coatings) from Claus Jurich, European Coatings Journal, April 2017.



Encapsulation and Coatings

Examples of benefit provided by micro-encapsulation:

• Protection of the payload:

– Compatibilisation of molecules incompatible with paint e.g. biocides or

corrosion inhibitors that would catalyse polymerisation reaction or destabilises the

paint formulation

– Protection of metallic pigment from chemical attacks (e.g. reaction in WB coatings)

• Sustained release

– Provide extended functionalities (Corrosion protection, anti-fouling, biocidal, etc…)

• Trigger Release:

– Self Healing materials dual and single capsule system.

• Incorporation of specific functionality requiring capsules geometry

– Phase Change Materials, etc…

6This document is the property of Ceramisphere Pty Ltd. No part shall be reproduced or transmitted without the express prior written authorisation from Ceramisphere Pty


CERAMISPHERE ENCAPSULATION

TECHNOLOGY

7

• Combination of emulsion and sol-gel chemistry:

• Emulsion provides compartmentalization of the active.

• Sol-gel process (inorganic poly-condensation) allows the formation of

ceramic matrix at room temperature.

Watch the movie at <http://youtu.be/d3VmumaiBtI>

8

What is Ceramisphere’s

Encapsulation Process?



9

• Ceramisphere process is a true encapsulation

process: Matrix is formed around the active

providing enhanced protection of the payload.

• Ceramisphere technology produces matrix

particles i.e. full sphere with the active

homogeneously distributed inside the pores NOT

capsules i.e. NOT ping pong balls.

Key Characteristics



10

• Matrix particles:

• High mechanical strength ⟹ compatibility with industrial post processing

(grinding, milling, extrusion)

• Better protection of the payload ⟹ Incorporation of actives which are

incompatible with the paint chemistry (accelerants, destabilising molecules,

etc..)

• Controllable release rate (Hours to years) ⟹ extend functionality in time

• Controllable particle size (10 nm to 100 µm) ⟹ compatibility with very thin

coatings and optical properties.

• Versatile ⟹ Encapsulate a wide range of actives e.g. water soluble and water

insoluble corrosion inhibitors

• Environmentally friendly, not toxic and biocompatible ⟹ important aspect for

regulatory affairs and marketing

• Can be produced in dry powder or slurry form ⟹ Use in various types of paints

powder coatings, water based etc…

Key Advantages for Coatings



Matrix Release

• In contrast to capsules (i.e. ping pong ball), when matrix particles (micro-

sponges) are crushed there is no significant difference in the release rate.

• Example: release of Rhodamine encapsulated in silica microparticles.

11

● Non Crushed

■ CrushedNon

Crushed

Crushed



Mechanical Resistance

• Inhibispheres are resistant

mechanically and can be grinded

(pearl mill) or even extruded (powder

coating)

• Mechanical properties of silica

microparticles (≈ 50 µm) measured by

nano-indentation:

• Average strength from 60-105 MPa

depending on composition and

synthesis conditions.

• Weibull modulus from 2-6.5 (m)

– The mechanical properties of

submicron hybrid silica particles are

not measurable but the particles

survive pearl mill and extrusion.

12

Inhibispheres inside a model varnish

This document is the property of Ceramisphere Pty Ltd. No part shall be reproduced or transmitted without the express prior written authorisation from Ceramisphere Pty Ltd, and the contents shall not be disclosed.

Compatibilisation

• Encapsulation of reactive molecules i.e. react with the

polymers in the paint or destabilise the paint formulation.

• Encapsulation makes them “invisible” to the paint.

• Potential to use new molecules to bring functionality to paints

and coatings.

13

Encapsulated

inhibitorUnencapsulated

inhibitor

Aging of encapsulated

vs unencapsulated

inhibitors in WB epoxy


Sustained Release

• Sustained release to extend protection in time.

14

15

Controlled Release

Large Mesopores

Small Micropores

1µm

1µm

• Controlled release is achieved through a precise control of the

internal nano-structure and composition of the matrix


16

• Release of molecules from the coating :

– Release kinetics from the coating depends on amount of inhibitors

incorporated inside the spheres as well as the chemistry of the spheres.

– Release kinetics can be tailored to avoid release in the pot and subsequent

phase separation.

Controlled Release in Coatings

Cells for measuring release from coatings Release from identical model coatings

containing particles with different release rate


Image courtesy of Airbus Innovations

Tailored Particle Size

≈ 20 µm ≈ 50 nm

Microparticles Submicron Particles Nanoparticles

• Particle size can be precisely controlled from 10 nm to 100 µm

• Particle size controlled by the emulsion droplet size

• Use of submicron particles for very thin coatings (e.g. wash primer ≈1-2µm)

This document is the property of Ceramisphere Pty Ltd. No part shall be reproduced or transmitted without the express prior

written authorisation from Ceramisphere Pty Ltd, and the contents shall not be disclosed.

≈ 0.5 µm

17

Optical Properties

• The particle size can be tailored so that the addition of Inhibispheres does

not interfere with optical properties of the coating.

• This means that they can be added to the top coat, providing functionality

properties while maintaining the gloss.

• Can be made small enough to be transparent.

18This document is the property of Ceramisphere Pty Ltd. No part shall be reproduced or transmitted without the express prior written authorisation from Ceramisphere Pty Ltd,

and the contents shall not be disclosed.

94.8

20.9

9994.7

0

10

20

30

40

50

60

70

80

90

100

Blank ZP10 (10%) ISM (2%) ISM (10%)

Glo

ss u

nits (

GU

)

Gloss of coatings with Inhibispheres

60 degree gloss



Sustained release corrosion Inhibition

Inhibispheres

19

20

Inhibispheres for Corrosion

Protection

• 10 year collaboration with Airbus Group Innovations

to replace the highly toxic Chromium VI in

aeronautical coatings by non-toxic controlled release

solution.

• Last 3 years, transitioned from a micro-encapsulation

company to a smart pigment manufacturer.

• Currently, moving beyond Aerospace into other

segments of the industrial coatings market.

• Starting to develop anti-fouling and biocidal

formulations.



Mode of Action



◉ Inhibispheres are porous silica particles

containing encapsulated corrosion inhibitors

and their payload is released by diffusion

through the porous silica matrix

◉ The spheres can be easily introduced in the

paint or coating formulation and are designed

to avoid leaching in the pot

◉ Inhibispheres which are homogeneously

dispersed inside the coating become activated,

either during the rupture of the coating (e.g.

cut), or by the presence of water in the paint

film during immersion or condensation

◉ The released inhibitors then diffuse rapidly to

the corrosion site

Product Range



• Currently have a range of 6 products:

– containing different inhibitors: 3 for steel and 3 for aluminium.

– with different release rates: fast (days), medium (weeks), slow (months)

• Can be used alone or in combinations (Inhibispheres cocktail)

• Can be used in combination with traditional “dumb” anticorrosion pigments

• The product range covers all different type of paints (solvent based, water

based and powder coating).

23

Sample Time

(h)

Creep area

(cm2)

Inhibispheres A

2%

500 3.177 (25%

less)

Traditional AC

Pigments 10%

500 4.201

Thickness = 75 µm

ASTM B117

Sand-blasted Steel

EN10130

2K Epoxy

Solvent based system

0.3% wt. inhibitor

Improved Performance with 30x less Inhibitor



10% Traditional AC pigments2% Inhibispheres A

Competitive Advantages

Efficient & Green

• Greener cost-effective solution:

– Due to their sustained released capability, the

Inhibispheres use significantly less active (10-

30 times less) for similar performance.

– In contrast to more traditional anticorrosion

pigments, incorporation of Inhibispheres inside

a paint will not attract additional safety labels

on the final product.

– With Inhibispheres, you can also produce

environmentally friendly coatings based on

purely organic inhibitors (metal free).

– Greener and future-proof formulation (future

regulatory changes)



Direct To Metal

• Potential simplification of paint system:

– The addition of Inhibispheres does not interfere with optical properties

– This means that they can be added to the top coat, providing

anticorrosive properties while maintaining the gloss

– Potentially replace two coats with a one coat system (direct-to-metal)

• Significant cost savings for the end-user

25

500 hr NSST on Steel

Commercial Primer (containing

10% ZnPO4) + Top coatTop Coat only

(containing 10% ISZB)

This document is the property of Ceramisphere Pty Ltd. No part shall be reproduced or transmitted without the express prior

written authorisation from Ceramisphere Pty Ltd, and the contents shall not be disclosed.

2 Coat-SystemCommercial Primer

& Top Coat

1 Coat-SystemTop Coat with

Inhibispheres

Extended Protection

• Extension of corrosion protection:

– Addition of Inhibispheres to existing

anticorrosion paint formulations can extend

the duration of the corrosion protection

without significant reformulation.

– Better performance with increasing amount

of Inhibispheres introduced in the primer

(which contains AC pigment)



2%0% 5% 10%

Commercial primer

containing ZnPO4 with

increasing amount of

Inhibispheres A.

Mild Steel 500h in NSST

Extended Protection

27

• Extension of corrosion protection:

– Addition of Inhibispheres to existing anticorrosion paint formulations help jump

corrosion classes C1 to C3 or C3 to C5 or C5+

– Reduce the number of coatings, thickness and weight for long term protection

2 Coat-SystemCommercial Primer

& Top Coat

C3

3 Coat-SystemCommercial

Primer,

thick epoxy

& Top Coat

C5

2 Coat-SystemTop Coat with

Inhibispheres

A. Noble-Judge,

C.Barbé, PCI

Magazine Feb 2019

28

“Self Healing”



System without Inhibispheres

• The defect is clearly visible since the

beginning of immersion

• The admittance values slightly increased

(resistance values decreased)

• Corrosion products in the scratch

System with Inhibispheres

• The defect is hardly seen

• The admittance values were much smaller

than the values observed for P0

• No corrosion products in the scratch

• Encapsulated inhibitors are gradually released

into the scratch to limit the corrosion process.

Demonstration of “Self Healing”

“Self Healing”

29



From C. da Silva, C. Barbé, E Campazzi, P-J. Lathière, N Pébère, E. Rumeau, L. Tran,

M. Villatte in the Proceeding of the 10th symposium on Electrochemical Methods in

Corrosion Research held in Maragogi

29

Key Competitive Advantages

Inhibispheres are a novel anticorrosion system with some unique advantages:

• Greener cost-effective solution: Inhibispheres use significantly less active (10-30

times less) for similar performance. No additional safety labels on the final product.

Potential metal-free formulations.

• Potential simplification of the paint system by adding directly anticorrosive

functionalities to the top coat without compromising optical quality

• Additive: Inhibispheres can be added to existing anticorrosion paint formulations to

extend the duration of the corrosion protection without significant reformulation.

• Compatibilisation: Encapsulation inside the Inhibispheres enables the use of

inhibitors which react with or destabilize the paint chemistry.

• Additional Bonus:

– survive milling, extrusion and other demanding processing steps.

– Do not affect the mechanical or chemical resistance properties of the coating.



Conclusions

31

• Micro-encapsulation can bring a wide range of benefits to coatings and paints

including the incorporation of incompatible molecules, the extension of functionality

through sustained release and the capacity for self healing.

• Paint manufacturing requires encapsulation systems with high mechanical, chemical

and thermal stability.

• Ceramisphere encapsulation technology provides such mechanical, chemical and

thermal stability. In addition:

– the particle size and release rates can be easily tailored to suit specific applications

(high-gloss & thin layers) and protection profile (extended protection).

– A wide range of chemicals (Hydrophobes and hydrophiles, big and small molecules

and even micron-size pigments) can be encapsulated providing flexibility for the

formulator.

– Environmentally friendly providing regulatory and marketing edge (Future proofing

formulation).

– Inhibispheres products are available in dry powder form through our local distributor

Silver Fern Chemicals (www.silverfernchemical.com/)



http://www.silverfernchemical.com/

32

Come and visit us

@ Table 90



Documents

Sustained Controlled Corrosion Inhibition...•Last 3 years, transitioned from a micro-encapsulation company to a smart pigment manufacturer. •Currently, moving beyond Aerospace