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What is nanodiamond (ND), methods of ND fabrication and

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▪ Introduction of the company

▪ What is nanodiamond (ND), methods of ND fabrication and Market overview

▪ Technology of Laser ND Synthesis

▪ ND surface modification and fabrication of slurries

▪ CARTHER project (CARbon nanoparticles for THERanostic applications)

▪ PANDA project (Production of Advanced Nano-Diamond Additives)

▪ Looking for partners

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1. Private Israeli company # 514305671

2. Established in August 2009 in Jerusalem, Israel

3. Scope: nanodiamond (ND) technologies

4. Website: www.nanodiamond.co.il

5. Member of Israel Association of Manufacturers

6. Licensed supplier of Israel Ministry of Defense

7. Employees: 6

Ray Techniques Ltd, Introduction

Boris Zousman,main developerof RAY technologies

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• The problems we solve

• ND powders in the Market are of non-constant quality,complicated to use in industrial scale and expensive;

• No industrial technologies for ND disaggregation & mixing;

• Insufficient number of validated ND formulations.

• Our mission is to provide consumers in various fields of industry,

energy, science & medicine with ready-to-use and efficient NDadditives to diverse materials and processes.

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▪ Synthesis of high-quality nanodiamond (ND) powder

▪ Uniform mixing of ND with diverse materials, manufacturing of stable ND colloids and powders with controlled surface chemistry

▪ Design novel ND-based composite materials with desired properties and ND masterbatches for their manufacturing

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Patents: “Method and system for controlled synthesis of

nanodiamonds”

Patents granted in USA and Japan.

Patent pending: in EU, South Korea and Israel.

Know-how: ND surface functionalization, fabrication of

nanocarbon colloids (including ND, graphene, fullerene, carbon nanotubes (CNT)

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• Diamond core (sp3) with average size of ~4 nano-meters having unique diamond properties

• Hybrid surface structure (sp2) with unpaired electrons

• Active surface shell of various functional groups containing O, H and N

Functional groups enable to attach ND to molecules of a chosen material,to transfer it unique features of diamond and improve its properties.

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Three-dimensional cubic lattice of tetrahedral bonded carbon atoms determine

unique properties of diamond:

• Extreme mechanical hardness 98 GPa {111}

• Highest wear resistance

• Outstanding optical & electronic properties

• Wide band gap {300 K}: 5.47 eV

• Refractive index: 2.419

• Highest thermal conductivity: 2300 W/mK

• Very high electrical insulation: 10¹³ ῼcm

• Highest sound propagation velocity

• Chemical and radiation resistance

• Biological compatibility and non- cytoxity

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Reinforcing polymer filler (glues & paints)

Fine polishing abrasive (magnetic disks?)

Additives in coatings (galvanic & Electroless)

Additive to lubricants (oils & greases)

Catalysts in chemistry & power applications

Ex

ist

ing

ND

ap

pli

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tio

ns

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Advanced ND applications are still under development:

✓ Thermal Management

✓ Energy storage

✓ Analytical chemistry

✓ Nano-composite materials with high radiation resistance

✓ Glass / polymer scratch protection

✓ High refractive index polymers

✓ Efficient catalysts

✓ Bio-Med: drug delivery / contrast agent for bio-imaging

1. Detonation of Explosives: commercially available

2. High-Pressure-High-Temperature (HPHT), crashed: commercially available

3. Chemical Vapor Deposition (CVD), crashed: not economical

4. Other methods of ND Synthesis: not economical

1) Ultrasonic Cavitation (UC)

2) Hydrothermal Synthesis (HTS)

3) Ion Bombardment (IB)

4) Pulse Laser Ablation in liquid (PLAL)

5. Light Hydro-Dynamic Pulse (LHDP) – RAY technology

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1. Non-consistency of ND quality & reactivity caused by ND structure& the current method of ND synthesis

2. Almost no industrial technologies for ND disaggregation & uniformmixing with various materials

3. Not enough final ND formulations: most advanced applications arestill under development

4. No fundamental understanding how ND concentration andstructure affect the performance of ND composites

5. No standards for the regulation of ND quality

6. No validation of the developed formulations by big potentialconsumers

Presently ND market is still in its initial stage.

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RAY Technology of ND Synthesis1

• In contrast to the existing technology the process is controllable, environment- friendly & non-hazardous

• Production at laboratory / pilot conditions

• Product of the best quality

• Patent protection

• Initial sales

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1• Preparation of carbon soot

from pure graphite

2• Forming special targets from

soot & wax

3• Laser treatment of special

targets in liquid

4• ND separation by flotation

method, washing & drying

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Nanodiamonds of high purity and homogeneity

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1. PurityIncombustible residue ND obtained by laser synthesis (RayND): 0 (less than the accuracy of the instrument - 0.02 wt %)For comparison: incombustible residue of DND: 0.4 - 8 wt. %

RayND powder is practically free of metals which is highly importantfor most advanced applications (electronics, neutrons, bio-medicine)

2. Diamond structure sp3 on ND surface in RayND up to 72 %; in DND 23 % of the surface area (XPS analysis)

3. Homogeneity

4. Controlled process → constancy of properties Possibility to provide desired ND features (crystalline size, opticproperties, surface chemistry and desired reactivity)

RAY has developed an industrial technology for introducing ND into various media. Special mechanical, thermal and chemical ND surface modification results in:

• Covalent bonding with matrix’ molecules (no surfactants!)

• ND disaggregation in diverse solvents

• Uniform distribution in basic material

• High efficiency of ND in the improving performance

RAY Technology of ND Modification2

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ND aggregate on the copper grid.Size: ~1.5 micron

To produce stable colloids ND should be disaggregated & functionalized.

Each material requires special ND surface modification to reach desired interaction between its molecules and ND particles.

ND Powder with Modified Surface 4-10 wt. % ND Suspensions (Slurries)

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Specially modified ND powders and slurries are compatible with somepolymers and solvents. They form stable suspensions with nearlydisaggregated diamond nanoparticles by regular mixing, not requiringadditional treatment and / or development.

Modified ND Powders

▪ Lyophobic (positive charge)

▪ Hydrophobic (alkylated)

▪ Hydrophilic (hydroxylated)

▪ Lyophilic (nitrogenized)

▪ Magnetic (Fe-doped)

▪ Magnetic (metal-free, outstanding magnetism)

ND Water Based Slurries

▪ Single particles @ 1.7 wt.%

▪ Hydroxyl groups @ 5 wt.% ND

▪ Nitrogenized @ 4 wt.% ND

▪ With surfactants @ 10 wt.%

Stable ND Slurries in Solvents

▪ Acetone @ 4 wt.% ND

▪ Isopropyl alcohol @ 4 wt.% ND

▪ Ethanol amine @ 5 wt.% ND

▪ N-methyl-2-pyrrolidine @ 5 wt.% ND

▪ Toluene @ 7 wt.% ND

▪ Cyclohexane @ 7 wt.% ND

▪ Xylene @ 7 wt.% ND

▪ Dimethylformamide @ 10 wt.% ND

▪ 2-Butoxyethanol @ 10 wt.% ND

ND Oil Slurries

▪ Polyester oil @ 3 wt. % ND

▪ Petroleum distillate @ 5 wt.% ND

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▪ Antifriction compounds

▪ Polishing products

▪ Thermal conductive polymer compounds

▪ Coolants for wafers dicing

▪ Seeds for CVD diamond coatings

▪ Galvanic electrolytes

▪ Epoxy and other polymer resins

RAY Final Products: Additives3

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Use ND lubricants for lapping /finishing results in significant decrease of the

friction coefficient and high energy savings

• Service life of friction pairs increase by a factor of 3 and more

• Decrease in energy & fuel consumption, around 10 % savings

• Enhanced horsepower and airproof capacity of engines

• Increase in reliability

• Decrease in noise

Physical mechanism:

• Fine polishing

• ND introduce within metal surfaces and create protective diamond nano-layer with high wear resistance

• ND in lubricant work as nano-bearings

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RT-Gel, polishingwater-based gel withhigh ND concentration

RT-Lap, ND paste fordiamond, sapphire, silicon,silicon carbide and othermaterials polishing

Manufacturers of crystals and wafers areinterested to increase in the productivityof the polishing process

RAY thermal compounds contain ND particles uniformly distributed in polymer matrix

Advantages:

• Low thermal resistance• High electrical resistivity• Stability of properties• Low weight• Easy to use and remove • High range of operating temperatures • Non-toxicity• Low price

1. NanoHeat thermal grease for electronics (ready)2. Heat conductive epoxy (15 -18 W/mK)3. Insulating heat conductive ceramics (280 W/mK)

(under development)

2 3

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1

Chipping and cracking caused by overheating when non-treated water for cooling is used

Lubricating coolant reduces hot & friction removing chips from the cutting zone

Coolant Material

RT-Cool-Si Silicon

RT-Cool-SiO2 Glass

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Advantages in comparison with the existing product:1) Quality: less micro-cracks and surface layer tensions 2) Tools durability: blade resource increases by 5 times3) Productivity: speed of dicing can be enhanced significantly 4) Wafer cost: reduces considerably

High quality CVD films grown using RayND precursor

Naval Research Laboratory & SAIC Inc., Washington: RayND was tested for seeding in the growth of nano-crystalline diamond films of different thickness (0.3, 0.5 and 2.0 microns) in an ASTEX 1.5 KW microwave plasma deposition system. The grown films exhibit a high level of quality.

Product Description Features

RayND-IPA-5 5 wt.% ND Isopropanol based slurry Surfactant-free

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Improvement in coating quality

1. Increase in wear resistance: 2-12 times

2. Increase in micro hardness:

Cr + ND: up to 1400-1500 kg/mm

Ni + ND: up to 800-900 kg/mm

Cu + ND: up to 160 kg/mm

Ag + ND: up to 180 kg/mm

Au + ND: up to 250 kg/mm

Al + ND: up to 600-700 kg/mm

3. Reduced porosity of the coating layer

4. Increase in elasticity

5. Improved corrosion resistance

6. 2-10 times increase in products durability

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Proposed solution

▪ Uniform dispersing specially modified ND within polymer matrix for improving mechanical, optical and thermal properties

▪ Synergic effect of using ND and other nanoparticles

Advantages

▪ Improved performance

▪ High reliability / durability: high aging resistance chemical, frost and radiation resistance, low thermal expansion (induced stresses) ensure layer consistency, no cracking

▪ Environment: non-toxic (RoHS requirements, simple utilization)

▪ Manufacturability: assembly ease; no special requirements for storage; low bond-line thickness & layer uniformity

▪ Cost effectiveness: ensure low cost of material

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CARTHER Project

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The goal: systematic interdisciplinary study of carbon-based nanomaterials (particularly ND) for theranostic application:

• Efficiency and specific localization in biological cells depending on surface chemistry

• Luminescent properties, photo-induced electrical and thermal effects

• Photo-excitation cancer therapy

• Design imaging therapeutic agents

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RAY motivation: Involvement in biomed researchDefinition of RayND advantages for bio-medicineNano-characterization opportunitiesExperience with H2020

Conclusion: Specially modified non-toxic NDs without therapeutics kill pancreatic cancer cells almost not affecting healthy tissue

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Without ND With ND

Cancer Pancreas Cell Line Panc01

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Magnetic-modified almost metal free ND were studied for targeted drug delivery. The goal was to combine advantages of ND and magnetic nanoparticles.

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L.-C. Liu, C.-Y. Song, Z.-R. Lin, Y.-C. Lin, A. Karmenyan, S. Norina, O. Levinson, B. Zousman, E. Perevedentseva, C.-L. Cheng; Annual Meeting of the Physical Society of the Republic of China, 2016

The magnetization curve of RayND-M (SQUID-VSM vibrating sample magnetometerPL spectra

RAY has proposed a new mechanism of therapy using ND.

▪ Nano-capsules 100 nm in size (most suitable for passive targeting) filled withND with an average size of 4 nm are invasively introduced into the body.

▪ The capsules move with blood flow through healthy tissues and are collectedin the intercellular space of inflammation area due to the size of 80-120 nm.

▪ Then capsule membranes are dissolved. The released NDs are absorbed bypathological cells freely penetrating through cell membranes.

▪ Some external impact harmless for healthy tissues (e.g. ultrasound orelectromagnetic) should be applied to cause rapid movement of ND insidethe cells or heating, resulting in mechanical / thermal destruction of cells.

▪ Then NDs leave the inflammation area with what's left of the pathologicalcells not affecting healthy tissues.

▪ The process can be controlled using existing in-vivo-imaging instrumentation.

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The frame: Horizon 2020 program H2020-SMEInst-2017

Phase 1: feasibility study and writing Business Plan

PANDA Project

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1. Full industrial technological chain for fabrication highly pure anduniform ND and efficient ND additives for

• Fine polishing (sapphire wafers, optical crystals, internal surfaces ofthin tubes)

• Lubricants• Various coatings• Diverse polymer compounds (improving wear, antiaging, radiation &

frost resistance, thermal conductivity and electrical resistivity, etc.)• Biomedicine (cancer treatment, early diagnostics, cell imaging)

2. Scaling of RAY technology and foundation of mass production

3. Business strategy and Business Plan

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▪ ND laser synthesis: advisability of scaling

1. Production capability more than 100 kg ND monthly

2. ND line should be operated by maximum 3 workers: sootproduction, target preparation and its delivery to the laserirradiation zone and post-synthesis treatment (isolation,washing & drying).

3. The key factor: possibility to optimize laser beam parametersincreasing in the output by the factor of 200.

▪ PANDA: principal design of 2 manufacturing lines: for ND synthesisand for manufacturing of ND additives

▪ Market research, business strategy and Business Plan

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▪ High-repetition rate (30 kHz) Q-switch laser with a disc amplifier▪ Calculated productivity: 600 g of pure ND per hour,▪ Targeted cost 400 $ / kg

1. Aggressive marketing: the first step 5 project / product managers: 1) polymers, 2) polishing slurries and pastes, 3) additives lubricants, 4) additives to galvanic and other coatings, 5) coordination of Biomed research, providing ND samples

2. Establishing PANDA Manufacturing Line for upgrading purchased ND and producing ready-to-use additives in the form of modified powders, slurries and masterbatches

3. Establishing Laser ND Manufacturing Line (LaND) for providing PANDA Line with raw material and bio-med research market

4. Development of novel ND-based products for various industries, patenting of final formulations & licensing

5. Participation in joint R&D programs in the field of ND applications with leading academia groups and industrial partners

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Consumers

Subcontractors

Joint venturesInvestors

SALES

R&D partners

• Unique RAY Technology

• Market demand in wide range of applications

• Already established contacts with leading players in the market

• Final products already developed and tested

• Promising preliminary results in new applications

• Various joint R&D opportunities => international researchcooperation programs

• Unique RT team expertise combination enabling implementationof various technological projects

• Unique combination DIAMOND + NANO + Israeli Start-up

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