SYNTHESIS OF THERMOREGULATING MICROCAPSULES AND …cytema.es/files/2014/02/Ana-María-Borreguero-Simón.pdf · ana m. borreguero, Ángel serrano, irene izarra, manuel carmona and

SYNTHESIS OF THERMOREGULATINGMICROCAPSULES AND THEIR APPLICATION

IN BUILDING MATERIALS

ANA M. BORREGUERO, ÁNGEL SERRANO, IRENE IZARRA, MANUEL CARMONA AND JUAN F. RODRÍGUEZ

II WORKSHOP CYTEMA

“EFICIENCIA ENERGÉTICA E INNOVACIÓN EN ENERGÍA RENOVABLE: HACIA UN NUEVO MODELO SOCIAL DE PRODUCCIÓN”

27th June, Ciudad Real, Spain

WORKSHOP “EFICIENCIA ENERGÉTICA E INNOVACIÓN EN ENERGÍA RENOVABLE: HACIA UN NUEVO MODELO SOCIAL DE PRODUCCIÓN”


FUNDING

2

- Desarrollo de Nuevo Conocimiento y Tecnología Inteligente MaterialesOrgánicos y Cerámicos, Orientado a la Mejora de la Productividad y laCreación de Negocio en el Ámbito de una Edificación más Sostenible(Proyecto Prometeo). Proyecto CENIT-ACCIONA. From 01/09/2006 to31/08/2009 (208.800 €)

- Acuerdo Marco de Colaboración para Investigación en MaterialesAvanzados y su Aplicación en Construcción. ACCIONA. From 19/12/2012to 06/08/2015 (41.818,18 €)

- New Advanced Insulation Phase Change Materials. NANOPCM. 7th FP -EUROPEAN COMMISSION (Ref. 260056). From 01/06/2010 to31/05/2013 (304.906,6 €).

- Nanocomposite for building constructions and civil infraestructures:European network pilot production line to promote industrial applicationcases. Nanoleap. H2020 - EUROPEAN COMMISSION (Ref. 646397).From 01/01/2015 to 30/06/2018 (6.878.350,00 €).



INTRODUCTION

3

European Directive on energy efficiency 2012/27/UE

o 40% Total energy consumptiono 36% CO2 Emission

Buildings

CURRENT SOLUTIONS

New building materials and designs

European Directive on the energy performance of buildings 2010/31/UE

Climate and Energy Targets

Fossil fuel Renewable Energies

Reduce in a 20% the Union’s primary energy consumption by 2020 compare to 1990



INTRODUCTION

4

ALTERNATIVE

PASSIVE SOLAR HEAT STORAGE

Inexhaustible source Free Large surface area of buildings

exposed to the sun

It needs to be absorbed, stored and released

ABSORB STORAGE RELEASE

PCMs(Phase Change Materials)

Applied

Building Materials



INTRODUCTION

5

How do PCMs work?

T Outside> T MeltingPCM melts

(Heat required)

T Outside< T MeltingPCM solidifies(Heat released)

HOT OUTSIDE

Heat Required

COOL OUTSIDE

Heat Released

INSIDE THE BUILDING TEMPERATURE REMAINS CLOSE TO THE MELTING POINT

Money spent in energy

consumptionEnvironmental

pollution

Energy consumption in heaters and air

conditioners

REDUCTION OF:REDUCTION OF:



INTRODUCTIONPCMS INCORPORATION IN BUILDINGS

• Building materials to incorporate PCMs:- Gypsum- Polyurethane foams - Concrete

• Ways of incorporating PCMs into building materials:- Direct incorporation- PCMs microencapsulation and further incorporation

• Properties of proper PCMs for applications in buildings- Melting temperature about 25ºC - High latent heat of fusion- Low cost - Good availability- Non-toxic - Non-corrosive



INTRODUCTIONPCMS INCORPORATION IN BUILDINGS

PCMs microencapsulation and further incorporation

SHELL: POLYMERS

- To avoid PCM interaction with the rest of building materials.- To avoid the PCM leakage when they remain liquid. - To give a high area of heat transfer.- Easy handling. - Microcapsules properties modification

MAIN REASONS FOR PCMS MICROENCAPSULATION:

-Low cost-Chemically inert respecting the building materials-Low density



Production of Microcapsulesat Lab Scale


27th June, Ciudad Real, Spain 9

Spray drying technique

Suspension polymerization

Gas for solvent evaporation

Feed

Gas + solvent Product

Patent: EP1828.2A

Patent: WO2007/107171 A1

MICROCAPSULES SYNTHESIS



MICROCAPSULES CHARACTERIZATION

-10 0 10 20 30 40-3

-2

-1

0

Hf=96,2 J/g

Hf=96,7 J/g

Inte

nsid

ad (u

.a.)

Temperature (ºC)

Material Original After thermal treatment

-10 0 10 20 30 40-4

-3

-2

-1

0

HfJ/g

HfJ/g

Inte

nsity

(u.a

.)

Temperatura (ºC)

Microcapsule Pure paraffin

Scanning Electron Microscopy (SEM)Low Angle Laser Light Scattering (LALLS)

Differential Scanning Calorimetry (DSC)



NANOPARTICLES ADDITION

mSD-RT27-ZnO mSD-RT27-CNFs mSD-RT27-Nanosilicon




Production of Microcapsulesat Pilot Plant Scale



SCALING UP

Centrifuge equipment

10 L glassreactor

Lab scale

2L glassreactor


1000 L glassreactor

Pilot plant scale



Feed Tank 500 mL Feed Tank 1200 LProduct

0.5 kg/d

10 kg/h

SCALING UPMICROCAPSULES SYNTHESIS



Applications



APPLICATION IN BUILDING MATERIALS

EXTERNAL

SHEET

RESIN

CORE (POLYURETHANE

FOAM)

PU Foams

Gypsum blocks

Microcapsules

Gypsum crystals

The aim of this work is to develop new materials exhibiting high TES capacity.



Gypsum



•Effect of Microcapsule Type•Different microencapsulated PCMs contents•Effect of the water content

•Crystal size•Porosity•Density•Mechanical Properties•Thermal analyses: Latent Heat or Thermal Energy Storage (TES) Capacity, Thermal conductivity•

OPTIMIZATION of the water/Hem ratioMaximum content of two types of microcapsules (MC-PS

y MC-SD)

For microcapsule contents above 15% the mixture becomes unwieldy, setting quickly and making the

manufacture of the samples impossible.

APPLICATION IN GYPSUM BLOCKS



Flowdirection Flow

direction

Input heat flux sensor

Output heat flux sensor

Output heat flux sensorOutput heatflux sensor

Upper Temp Upper Temp

Center Temp

Down Temp Down TempCenter Temp

Aluminium cellHot side

THERMAL BEHAVIOUREXPERIMENTAL SET UP

APPLICATION IN PU FOAMS

Thermal treatment: Cell temperature change from 18 to 40ºC



↑ MC Content

↓ T transition stateEffect of PCM

Thermal Results Using MC-SP

0 5000 10000 15000 20000 25000

18

20

22

24

26

28

30

32

Tem

pera

ture

؛) C

)time (sec)

0 15 45 50

% SP Microcapsules

0.8 water/Hem

0 5000 10000 15000 20000

18

20

22

24

26

28

30

32

Tem

pera

ture

؛) C

)

time (sec)

0 15 20

% SP Microcapsules

0.57 water/Hem

↑ MC Content

↓ T stationary state

0 5000 10000 15000 20000

18

20

22

24

26

28

30

32

Tem

pera

ture

؛) C

)

time (sec)

0 15 30

% SP Microcapsules

0.7 water/Hem


Maximum content = 45%wt



↑ MC Content

↓ T transition state

↑ MC Content

↓ T stationary state

Thermal Results Using MC-SD

0 5000 10000 15000 20000

18

20

22

24

26

28

30

32

Tem

pera

ture

؛) C

)

time (sec)

0 30 SD 35 SD

% SD Microcapsules

0.7 water/Hem

0 5000 10000 15000 20000 25000

18

20

22

24

26

28

30

32

0.8 water/Hem

Tem

pera

ture

؛) C

)

time (sec)

0 15 40 50

% SD Microcapsules

0 5000 10000 15000 20000

18

20

22

24

26

28

30

Tem

pera

ture

؛) C

)

time (sec)

0 40 55

% SD Microcapsules

0.9 water/Hem


Maximum content = 55%wt



Study of input and outpus heat flows in

order to determine the accumulated heat

‐50

0

50

100

150

200

250

0 5000 10000 15000 20000 25000

Heatflows(W/m

2 )

Time (sec)

Heat Flows

q out5

q out6

q in7

q in 12

0

0,2

0,4

0,6

0,8

1

1,2

1,4

0 5000 10000 15000 20000 25000Q (w

)Time (sec)

Accumulation

0 5000 10000 15000 20000

20

24

28

32

36

Tdow

n C؛)

)

time (sec)

Tdown Tmiddle Ttop

0.9 Water/Hem 55% SD Microcapsules




Thermal Capacity MC-SD and MC-SPThermal Capacity MC-SD and MC-SP

↑MC/Hem = ↑Cp

0 10 20 30 40 50 600.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

0.7 SD 0.8 SD 0.9 SD 0.57 SP 0.65 SP 0.7 SP 0.8 SP Linear Fit of SD Linear Fit of SP

(J/gC؛

)

Microcapsule (%)




3.6 1063.6 106

1m3 of gypsum boards with water/Hem ratio of 0.7 and 35% of MC-SD

Due to the microcapsules:Savings of 10,56 kWh/operating cycle

0.35 kg CO2/ kWh(CNE, 2010)

Reduction of 3,7 kg CO2emissions/operating cycle




PU Foams



n O=C=N-R–N=C=O + n HO-R’-OHPolyisocyanate Polyol Polyurethane

[-CO-NH-R–NH-CO-O-R’-O-] n

Polyol

Additives:blowing agent (Water), surfactant (Tegostab 8404), catalyst (Tegoamin BDE)

PCMs

Mix

Polyisocyanate

Different microencapsulated

PCMs contentsUp to a 50 wt%

• Microcapsules distribution•Rising process•Latent Heat or Thermal Energy Storage (TES) Capacity• Foam structure and cell size• Density• Mechanical properties

Microencapsulated PCMs are stable in polyisocyante and poliol




THERMAL CHARACTERIZATION - DSC

-0,45

-0,4

-0,35

-0,3

-0,25

-0,2

-0,15

-0,1

-0,05

0

-10 0 10 20 30 40 50 60 70

Inte

nsity

(u.a

)

Temperature (ºC)

0% Middle

10% Middle

20% Middle

30% Middle

40% Middle

50% Middle

% PCM QDOWN(J/g)

QMIDDLE(J/g)

QUP(J/g)

QEXP(J/g)

QTH(J/g)

0 0 0 0 0 010 7,46 7,014 7,77 7,41 8,5820 16,57 15,82 16,71 16,37 17,1630 26,49 25,44 24,57 25,50 25,7440 36,52 33,82 32,9 34,41 34,3250 39,21 40,57 37,31 39,03 42,91

3

1

3

1exp

··

iii

iii

i

erimental

V

VQQ

Microcapsules were homogeneously distributed into the whole foam

Microcapsules Content (%wt)

Latent Heat

)(gWeightFoam(g)masslesmicrocapsu(J/g)Q

(J/g)Q lesmicrocápsultheoretica

Hf=40.57 J/gT=23.5ºC

DSC analyses




Similar temperatures at stationary condition, but

big difference in the transition step

15

20

25

30

35

40

0 5000 10000 15000 20000

Tem

pera

ture

(ºC

)

t (s)

Tup average 0%

Tup average 10%

Tup average 20%

Tup average 30%

Tup average 40%

Tup average 50%

Tbath

External Temperature

Melting of PCM by energyabsorption

THERMAL BEHAVIOUR EXPERIMENTAL SET UPAPPLICATION IN PU FOAMS




3.6 1063.6 106

1m3 of PU foam boards with a 50% of MC-SD)

Due to the microcapsules:Savings of 5,4 kWh/operating cycle

0.35 kg CO2/ kWh(CNE, 2010)

Reduction of 1,9 kg CO2emissions/operating cycle



Conclusions



CONCLUSIONS

Besides, these use of thesematerials in buildings contributeto reduce the CO2 emissions

These composite materials allow tosave energy by absorbing andreleasing the solar energy

Two different processes for the PCMs microencapsulation have beensuccessfully developed and scaled up, showing their feasibility for anindustrial scale.The incorporation of these microcapsules into gypsum and PU foamsimproved the TES capacity of these materials.



Thank you for your attention

AcknowledgmentsAcciona Infraestructuras S.A.

Spanish Ministry of Science and InnovationThe European Commission

SYNTHESIS OF THERMOREGULATINGMICROCAPSULES AND THEIR APPLICATION

IN BUILDING MATERIALS

Documents

SYNTHESIS OF THERMOREGULATING MICROCAPSULES AND …cytema.es/files/2014/02/Ana-María-Borreguero-Simón.pdf · ana m. borreguero, Ángel serrano, irene izarra, manuel carmona and