COMUNICAÇÃO TÉCNICA ______________________________________________________________________________________________________________________________________________________________________________________________________

Nº 176452

Microfluidics Mario Ricardo Gongora-Rubio

Slides apresentado da Palestra da 5.Semana de Inovação, Belo Horizonte, 2019. – FPT Industrial

A série “Comunicação Técnica” compreende trabalhos elaborados por técnicos do IPT, apresentados em eventos, publicados em revistas especializadas ou quando seu conteúdo apresentar relevância pública. ___________________________________________________________________________________________________

Instituto de Pesquisas Tecnológicas do Estado de São Paulo

S/A - IPT Av. Prof. Almeida Prado, 532 | Cidade Universitária ou

Caixa Postal 0141 | CEP 01064-970 São Paulo | SP | Brasil | CEP 05508-901

Tel 11 3767 4374/4000 | Fax 11 3767-4099

www.ipt.br

Eng. Dr. Mário Ricardo Gongora Rubio

Senior Researcher

Micromanufacturing Laboratory

Institute for Technological Research (IPT)

Belo Horizonte - 2019

FTP Innovation Day - CNH Industrial

OUTLINE

IPT Presentation

Bionanomanufacturing Center

Technological Platforms & LMI Infrastructure

What is Microfluidics

Microfluids Phenomena

Microfluidic Unit Operations

Applications in Microreactors

Application in Energy and Automotive Industry

Conclusions

WHO WE ARE

One of the first applied R&D&I institutions in Brazil

Company controlled by São Paulo State Treasury Office - State of São Paulo Government.

TECHNICAL ACTIVITIES

Innovation, research and development

Technological Services Development and metrological support Information and technology education

TECHNICAL CENTERS

CT-Obras Center for Infrastructure Work Technology

CTMM Center for Technology in Metallurgy and Materials

CTGeo Center for Geoenvironmental Technologies

CT-Floresta Center for Forest Resource Technology

CTMetro Center for Mechanical, Electrical and Fluid Flow Metrology

CQuiM Center for Chemistry and Manufactured Goods

CIAM Center for Information Technology, Automation and Mobility

CETAC Center for the Built Environment

CTMNE Center for Mechanical, Naval and Electrical Technologies

NT- BIONANO Nucleus for Bionanomanufacturing

NT – MPE Nucleus for Technological Support to Medium and to Small Enterprises

LEL Light Weight Laboratory

INFRASTRUCTURE

• IPT units in: – São Paulo

– Franca (individual protection equipment))

– São José dos Campos* (composite materials)

14 technology centers

40 laboratories

103.523 m2 of labs area

240.000 m2 of total area

MARKETS

Transportation Infrastructure

Roads

Naval

Pipeline

Metro-railway

Airspace

Cargo

IT & ITS

Metallurgy

Chemistry

Bioproducts

Plastics & Rubber

Composites

Textiles & Leather

Wood

Energy Materials and

Chemistry

Civil Works

Buildings

Environmental

Impacts

Mining

Oil and gas

Ethanol

SOME CUSTOMERS

BIONANOMANUFACTURING CENTER

BIONANOMANUFACTURING CENTER LPP - Lab. Chemical Processes and Particle Technology Nanotechnology and advanced chemical processes LBI - Laboratory of Industrial Biotechnology Development and characterization of biotechnological solutions LMI - Micromanufacturing Lab. Miniaturization of products and processes

TECHNOLOGICAL PLATFORMS &

LMI INFRASTRUCTURE

TECHNOLOGICAL PLATFORMS

Nanotechnology: new possibilities of process intensification (physical, chemical & biological) through scale reduction with gains in product quality

Biotechnology: less aggressive processes to the environment with lower energy consumption and using renewable raw materials

Microtechnology: manufacturing capability for production of miniaturized devices and systems such as microsensors, microreactors and MEMS

LMI/IPT - INFRASTRUCTURE

Microfabrication in Clean Room Technology Equipment Lithography - Mask Aligner EVG620 - Spinner, hot plate, developer Brewer CEE - Maskless Laser Photolithography - Heilderberg µPG 501 Thin Film Deposition - PVD System KJLCLab18 - PECVD Oxford Plasmalab 80 Parylene coater SCS Labcoater 2 Wet Processes - Wafer cleaning bench - Wet Corrosion Bench - HF Vapor phase etcher Dry Corrosion - DRIE-ICP Oxford Plasmalab 100 - Plasma cleaner Diener Nano Wafer Processing - Wafer Bonder AML-AWB -CMP Logitech CM 61 Orbis - Wafer Dicing ADT 7100 Microscopy & Metrology - MEV Zeiss EVO MA 10 - EDS Brucker Quantax 200 - Profilemeter Brucker DEKTAK XT

LMI - MICROMANUFACTURING LAB (CLEAN ROOM)

LMI - MICROMANUFACTURING LAB (CLEAN ROOM)

Interdigital Sensor Application

4 µm gap

Micromachining (Laser)

Thick Film Deposition (Screen Printer)

Lamination

Sintering

Dicing

LTCC Micromixing Device and its internal geometry

LTCC PROCESS AT LMI

LTCC ADVANTAGES FOR MICROSYSTEMS

• Simplicity of tape machining in the green state with feature size of 50 m to several mm;

• Ability of 3D multilayering and high layer count;

• Integration of a wide range of materials with different properties & technologies;

• Adaptability of embedded passive structures;

• 3D Microfluidics are readily implemented;

• Tapes of different compositions can be formulated to obtain desired layer properties;

• Integrated Electronic circuits because of its hybrid nature;

• Possibility of auto-packed devices fabrication;

• Mass production methods can be readily applied;

• Fabrication techniques are relatively simple, inexpensive and environmentally benign.

LMI/IPT – LTCC INFRASTRUCTURE

Equipment for fabrication of LTCC devices:

– Laser Machining

– Screen Printing

– Uniaxial Laminator

– Sintering Oven

– Paste dispenser

– Rework equipment

Micro-

System

Module

TECHNOLOGY VISION

Actuator Micro

Fluidics

I/O

• Microsystems containing Sensors + actuators + Microfluidics & Electronics are feasible to integrate using the LTCC technology.

• The photograph shows a remote controlled microsystem for thermal actuation.

LTCC INTEGRATED MICROSYSTEMS

INITIAL LTCC RESEARCH

S&A Paper published in 2001 with more than 500 citations.

WHAT IS MICROFLUIDICS

MICROFLUIDICS

Behavior of fluids in Microscale: • Control of small fluid volumes,

• Low thermal mass & Fast response time,

• Reaction condition well controlled,

• Efficient mass transport,

• Low energy consumption,

• Continuous processes & Small systems size,

• Laminar flow allows controlled mixing

• Large surface to volume ratio

Microfluidics is a technology which refers to the research

and development of micro-scale devices which handle

small volumes of fluids (as small as micro-, nano-, pico

and even femtolitre volumes)

Some Advantages • Low fluid volumes consumption (less waste, lower reagents costs

and less required sample volumes),

• Faster analysis and response times due to short diffusion distances, fast heating, high surface to volume ratios, small heat capacities,

• Better process control because of a faster response of the system (e.g. thermal control for exothermic chemical reactions),

• Compactness of the systems due to integration of much functionality and small volumes,

• Massive parallelization due to compactness, which allows high throughput production,

• Cost-effective fabrication, allowing disposable devices, fabricated in mass production,

• Safer chemical, energy or biological studies because of integration of functionality, smaller fluid volumes and stored energies.

Traditional

Laboratory

Microfluidic

“Lab-on-

a-chip”

Cost Often very high Low Cost

Equipment Specialized

equipment

Integration on

chip

Time to get

results

Significant time Quick

Benefits of Microfluidics

MICROFLUIDICS SPECTRUM

TODAY MAIN APPLICATIONS

MICROFLUIDICS FABRICATION METHODS

• Soft Lithography

• Silicon Micromachining

• Glass Micromachining

• Plastic Micro-Injection Molding

• 3D Printing

• Green Tape Ceramics (LTCC) Structuring

BATCH Vs. FLOW

MICROREACTOR SCALE-UP

MICROFLUIDS PHENOMENA

LAMINAR AND TURBULENT FLOW

Unstable streamlines

mix fluids in random

and chaotic manner

Well defined streamlines

-adjacent horizontal layers

flow at different speeds

- zero flow at the solid-fluid

interface (no slip condition)

PRESSURE-DRIVEN FLOW

MICROFLUIDS PHENOMENA

Capillarity Surface tension

ElectroWetting Inertial Forces

The force on the fluid

due to a curved

streamline points outwards centrifugally.

DROP GENERATION

• Several structures are used as drop generators with monodisperse dispersion

HYDRODYNAMIC FOCUSING

• Hydrodynamic focusing can be used as drop generator allowing drop frequency and size.

3D FLOW FOCUSING

• 3D Flow focusing can be used to

implement the in-Flow

nanoprecipitation process

MICROFLUIDICS OPERATIONS

MICROFLUIDIC OPERATIONS

MICROMIXING

MIXING PRINCIPLES

Baker transformation as an example of Chaotic

Advection Mixing

3D MICRO MIXERS IN LTCC 3D Serpentine Micromixers can be used for chemical Microreactors in order to fabricate emulsions, particle encapsulation and nanomaterial fabrication

10 mm

MICROFLUÍDIC DEVICES

Aumento 10X Aumento 4X

TURRAX

EMULSIONS USING MICROFLUIDICS

Simple Emulsion Double Emulsion

EMULSION GENERATION

EMULSION PRODUCTION WITH MICROMIXERS • Micromixers can be used to produce emulsions to scale-up the

process in higher flow rates.

Crossing Channels geometry for Micromixer emulsion generator

Straight forward scale-out from bench to industrial

production due to the possibility of mass parallel module

integration to obtain production volume.

EMULSION PRODUCTION USING MICROMIXERS

Scale-Up Scale-out

MICROSEPARATION

SEPARATION TECHNIQUES

SEPARATION VIA LATERAL DISPLACEMENT MAGNETIC SEPARATIONS

GRAVITY SEPARATIONS SEPARATIONS IN PINCHED MICROCHANNELS

APPLICATIONS IN MICROREACTORS

FLOW CHEMISTRY

In flow chemistry, reagents are continuously pumped through the reactor and the product is continuously collected.

A

B

C

Syrris

BATCH AND FLOW

Classic way to do chemistry. • Reagents are loaded into the reactor,

mixed and left to react. • The products is collected at the end, after

the reaction has been completed and worked-up.

New technique. • Reagents streams are continuously

pumped into the flow reactor. • Reagents mix and react in the flow

reactor. • The product leaves the reactor as a

continuous stream. Key factors:

- Concentration - Mixing - Temperature - Reaction time

Key factors: - Residence time (flow rates) - Mixing - Pressure - Temperature

Reaction

Mixture

>5mm

Reagent A Reagent

B

Reagent A

Reaction

Mixture

~100µm

Reagent B

Syrris

FLOW CHEMISTRY PARAMETERS Residence time It can be defined as the time that every fraction of the reaction volume spends in the reactor.

Residence time is equivalent to reaction time in batch chemistry. It is calculated as follows:

Residence Time = Reactor Volume / Flow Rate

There are two ways of controlling the residence time:

• Vary the reactor volume

• Vary the flow rates.

Mixing • In flow chemistry mixing can be turbulent or laminar

Pressure • In a flow reactor the total pressure at any location is made up of two factors:

• Back pressure due to flow & Back pressure intentionally applied

Temperature • Due to a higher surface area to volume ratio, flow reactors enable better heat

transfer and therefore better temperature control.

Syrris

LTCC MICROHEAT EXCHANGE

The major advantage of microchannel heat sinks is the high heat transfer coefficients, up to 60 times higher than the heat transfer coefficient of conventional, macro scale heat exchangers.

• High heat transfer coefficients • Low thermal resistance • High aspect ratios • Occupy less space • Best suited for hot-spots • Increasing the aspect ratio will enhance

the convective heat transfer at fixed flow velocity

ADVANTAGES

Layers

Microchannels

Micro heat exchanger

DEVICE CONCEPT AND IMPLEMENTATION

Vásquez-Alvarez E. ; DegasperI, F. T. ; Morita, L. G. ; Gongora-Rubio M. R. ; Giudici, R. Development Of A Micro Heat Exchanger With Stacked Plates Using LTCC Technology. Brazilian Journal of Chemical Engineering, v. 27, p. 483497, 2010.

HEAT EXCHANGER FLOW ANALYSIS

Several entrance geometries studied

Velocity Results

DROP MICROREACTORS

• New methods for obtaining spatially separated drops for later electro-coalescence allow to perform functions such as Micro-precipitation.

• Extraction of iron oxide nanoparticles in extremely fast reactions.

Active Pharmaceutical

Ingredient (API)

Solubilization Nanoparticle

Formation

Increased bio-availability of poorly soluble drugs

MICROREACTORS FOR NANOPARTICLE PRODUCTION

Crystals Microfluidic device

Characterization

Amorphous Nanoparticles

ϕ ≈ 200 nm

APPLICATIONS IN ENERGY AND AUTOMOTIVE INDUSTRIES

BIODIESEL PRODUCTION IN MICROREACTORS

• Biodiesel is a biodegradable derivative fuel obtained from natural renewable resources. Several processes such cracking, esterification or transesterification can be used and it is produced from animal fats or vegetal oils.

• Several Brazilian vegetal species can be used, such as “mamona”, “dendê” (palm), sunflower, “babaçu”, peanut, tame nut and soy, as raw materials for the process.

Soy Oil

MICROFLUIDICS APPLIED TO BIODIESEL FABRICATION

Methanol

Transesterification Process Biodiesel +

Glycerin

Otimization of Micromixers

LTCC DEVICE FOR BIODIESEL

Microdevices in LTCC technology for the production of Biodiesel using the transesterification process with homogeneous or heterogenous catalyst.

Raw Materials

(oil &alcohol) +

catalyzer

Injection

System

Microreator &

Residence Time

control

Purification System

Measurement and

Control System

Separation System

Glycerin

Biodiesel

Excess

Microfluidic Device for Microreactor

Residence time and heater Microfluidic Module

WATER IN DIESEL EMULSIONS

• The presence of water nanodroplets in diesel causes micro explosions in combustion process; increase the presence of oxygen and in consequence will enhance the fuel performance.

• It was also demonstrated that small amounts of water nanodroplets, something like 5 up to 14%, can reduce the NO, NOx and CO2 emission in a range of 18%

• Water is immiscible in diesel oil and is not possible to obtain an emulsion without the use of a surfactant.

• It is important to use adequate surfactants concentrations to maintain the diesel with the same physical characteristics in terms of energy efficiency.

LTCC DEVICE FOR WATER IN DIESEL EMULSION

Vortex microfluidic device

0

100

200

300

400

500

600

8 10 12 16 20

Pa

rtic

le S

izes

(n

m)

Diesel Flow Rate (mL/min)

10%

5%

Water-in-diesel emulsion: water droplets size in function of diesel flow rate for two surfactant concentration (5 and 10 % v/v).

Particle sizes measurements: results obtained for a solution with 10 % of surfactant

Vortex microfluidic device fabricated in LTCC

OTHER MICROFLUIDICS APPLICATIONS

Reformer MICROFLUIDIC FUEL CELLS

A fuel processor and integrated fuel cell including a

monolithic three-dimensional multilayer ceramic

carrier Structure defining a fuel reformer and including

an integrated fuel cell stack. The reformer includes a

vaporization Zone, a reaction zone including a catalyst,

and an integrated heater. US 6,569,553 B1

A microfluidic vanadium fuel cell system employs graphite rods

commonly used as electrodes. The rods are mounted in a

hexagonal array comprising 12 anodes and 12 cathodes that

share the same fuel and oxidant channel. In this configuration,

the electrodes are connected both fluidically and electrically in

parallel. Connecting the cells electrically in series to achieve

higher voltages. DOI: 10.2478/s13531-011-0012-y

CONCLUSIONS

• At this time, several applications of Microfluidics in various areas of industrial technology were presented.

• We showed as well some applications in Microreactors, Energy and Automotive Industry.

• Microfluidics have been shown to be suitable for the integration of unitary micro-operations (such as mixing, dispensing, separating, diluting, microreacting and analyzing) generating complex functions in continuous flow, creating excellent opportunities for new developments.

LMI/IPT - Team Beatriz Nogueira Messias de Miranda, PhD Chemistry, IQSC, USP 2018

Luciana Ramos, Ph.D. in Mechanical Engineering, U of Michigan, 2005

Mário R. Gongora-Rubio, Ph.D. in Electrical Engineering, USP, 1999

Bruno Verona, B.Sc. in Electrical Engineering, USP, 2013

Martha Lucia Mora Bejarano, Dr. Chemical Engineering, USP, 2003

Karina Ferreira de Noronha Cruz, Dr. Materials Eng. UNIFESP, 2016

Aline Furtado Oliveira, Dr. Chemical Engineering, UNICAMP, 2018

Jaqueline Falchi Rocha, New Talent Program, MSc student at Mackenzie University

Roberta Cardoso, Visiting Researcher, Ph.D. IQ-USP

Ariel Pereira Lima, LTCC technology Trainee

Gabriel Antonieto Gianvecchio, Mechanical Engineering Trainee

Henrique Reis Wisinewski, MicrofabricationTrainee

6

gongoram@ipt.br