Performance improvement and innovation: the role of ... · Performance improvement and innovation: the role of nanotechnologies. ... CEI 20-34/3-2. ... CEI 20-37. mg/g. REFERENCE

an platform

Performance improvement and innovation: the role of nanotechnologiesEnrico BoccaleriAssociate Professor, Ph.D. Università del Piemonte Orientale - ITALY

CONTENT

1. Nanomaterials: an introduction

2. Experimental plan for PVC nanocomposites for cables

3. Thermal behaviour of PVC nanocomposites for cables

4. Stabilisation and HCl evolution

5. Perspectives & Conclusions

3 TITLE

Nanomaterials at a glance

Filler dimensions:Macro mmMicro µmNano nm

Form factor:3D Particles (nano-oxides, POSS)

2D Nanotubes

1D Layered materials (clays, hydroxides and hydrotalcites, phosphates, phosphonates)

4 TITLE

Materials in this work

Layered hydroxides• Cost effective• Can develop high surface area• Can be tailored in the properties• Can deliver manifold features to PVC

Clay-based materials• Cost effective for natural systems,

expensive if fully synthetic• Can develop high surface area• Can be tailored in the properties• Mainly developed/used in other

matrices than PVC

5 TITLE

Materials in this work

• POSS are actual 3D nanostructured hybrid materials• General formula (RSiO1.5)n

• Each Si atom is bound to:• One and a half atoms of Oxygen (sesquioss-)• An organic group (-ane)

Compatibilità organica e diminuzione viscosità

Sta

bili

tà c

him

ica

e el

evat

a ri

gidi

tà

6 TITLE

Materials in this workOpen cage systems

with high reactivity with surfaces and materials

Metal-containing materialsfor distributed catalytically

active sites

7 TITLE

How this stuff works…?

• Organic-inorganic hybrids : chemical approach

• Nanocomposites: physical approach

Dispersion of nanostructured particles in an organicmatrix (i.e. polymer), based on chemical affinity andinterfacial interactions between the two phases

Covalently bound structures interacting at molecularlevel (co-polymer, grafting, reactive processing)

8 TITLE

Going to nano scale….

• “bulk” effects dominate the final properties• Modeling of the features refer to mean material

properties• Interfacial effects are quite negligible• The final properties of a compound is described

by the sum of the features of the components

“Macro” fillers in polymers• Dispersion issues• Influence of mechanical features• Optical properties (i.e. reduction of

transparency, haze, gloss…)• Aesthetic features• Durability• Processing issues (loading, flow, melt

strength….)• Weight increase• Barrier effect• Physical aspects

Why???

9 TITLE

Going to nano scale….“Macro” fillers in polymers

• Final properties are related to effectsoperating at nanoscale level

• Surface and interfacial effects are crucial• The final properties are not related to the

basic features of the components but to the capability and type of interactions they give

• Surface/volume and surface/mass ratio are relevant

• Dispersion issues• Influence of mechanical features• Optical properties (i.e. reduction of

transparency, haze, gloss…)• Aesthetic features• Durability• Processing issues (loading, flow, melt

strength….)• Weight increase• Barrier effect• Physical aspects

“Nano” fillers in polymers

10 TITLE

Experimental plan for PVC cables

General purposes:

- Use of commercial grade matrices (cable-grade PVC formulation)

- Use of market-ready nanoadditives (no lab scale quantities)

- Use of industrial(-like) equipment for polymer treatment

- Afford the maximum performances vs. additive concentration (0.3 to 10 phr)

- Avoid umpairing other features (i.e. processability, flow etc….)

- Evaluate synergistic effects among nanostructured additives

- Use the experimental results to create background knowledge and understanding

11 TITLE

Experimental plan for PVC cables

Dry blending

NanofillersConcentrations rangingbetween 0.3 to 2.5 phr

PVC for cablesDry Blend

Extrusion

PVC K.70 phr 100

Coated CaCO3 (AtomforS) phr 75

DINP non stab. phr 50

Chloroparaffins (52%) phr 18

Calcium Stearate phr 1,5

Zinc Stearate phr 0,4

Soybeans oil epox phr 4

Realube RL105 phr 0,7

Stearic Acid phr 0,3

Irganox 1010 phr 0,2

Sb2O3 phr 4

+

Fireproof insulators

Twin screw co-rotating extruder• TM 20 HT – Maris• L/D = 40•D/d ratio = 1,55• Screw prof. = 3,5 mm• Output: pellet 4 mm• Air coolling• Feed rate: 3-7 kg/h

• XRD• TGA• SEM• Density• MFI• Color – LAB• Mechanical prop.• Hardness• Thermal stability (80°C - 7gg)• Xn test (250 e 500 h)• HCl evolution• Fire behaviour: UL94/LOI

Characterisation

12 TITLE

Thermal behaviour (TGA)

POSS presence modifies the thermal behaviour of the materials:- Delay of the degradation onset (chemical effect)- Modification of the degradation profiles (stabilisation

of labile sites)Different nanoadditives give a different effect

T = 50-800°C 10°C/min – Ar flow

REFERENCEPOSS1 0,62POSS2 0,62POSS3 0,62POSS4 0,62

13 TITLE


A synergistic role of POSS can be highlighted, globally reducing and delaying the decomposition and HClevolution

A nanoadditive (0,31 to 1,25 phr) can modify the degradation of PVC especiallyafter the onset of the first degradation

T = 50-800°C 10°C/min – Ar flow

ReferenceInorg (0,31)Inorg (0,31)/POSS1 (0,62)

ReferenceInorg (0,31)/POSS1 (0,62)Inorg (0,62)/POSS1 (0,62)Inorg (1,25)/POSS1 (0,62)

14 TITLE


The synergy of POSS with layered materials results in evident changes involving:-labile sites stabilisation- HCl scavenging- Condensed phase catalysis

T = 50-800°C 10°C/min – Ar flow

ReferenceHTLC (5)/POSS1 (0,62)HTLC (5)/POSS3 (0,62)Clay (2,5)/POSS A (0,62)

The decomposition profile is deeply modified in:• The onset of the degradation• The amount of weight loss• The temperature of occurence of degradation• The kinetics of degradation

15 TITLE

What says the literature…..Attività espletate - Analisi termica TGA e meccanismo di degradazione

The preliminary decomposition of PVC is due to “labile sites” thatcan be generated during processing, recycling or use that break producing HCl and give rise, at higher temperature, to an avalanche effect (secondary dehydrochlorination).The presence of cross-linking and compact chain domains can reduce this initiation process.

16 TITLE

Thermal stability# MATERIAL Formulation Density Hardness Thermal stability Th. Stab after

80°Cx168 h LOI

ISO 1183 ISO 868 CEI 20-34/3-2 CEI 20-34/3-2 CEI 20-22/4g/ml Sh A 15’’ minutes minutes %

1 REFERENCE 1,479 80,0 40 24,52 Inorganic 0,31 phr 1,480 77,5 40 25,53 Inorganic 0,62 phr 1,481 77,5 45 25,5

4 Inorganic 0,31 phr/POSS 0,62 phr

1,480 77,0 55 25,5

5 Inorganic 0,62 phr/POSS 0,62 phr

1,479 78,0 55 25,0

10 POSS1 0,62 phr 1,472 77,5 45 25,011 POSS2 0,62 phr 1,474 78,0 40 25,512 POSS3 0,62 phr 1,473 81,0 40 25,013 POSS4 0,62 phr 1,470 79,5 60 35 25,5

14 Clay 2,5 phr/POSS1 0,62 phr 1,484 81,0 55 25,0

15 HTLC 5 phr/POSS1 0,62 phr 1,493 80,0 165 140 25,5

16 Inorganic 1,25 phr/POSS1 0,62 phr

1,477 77,0 40 35 25,0

17 HTLC 5 phr/POSS1 0,62 phr 1,486 81,5 165 140 25,5

18 HTLC 5 phr 1,498 82,0 165 140 26,019 HTLC2 1,25 phr 1,484 80,0 40 37 25,0

17 TITLE

Designing new formulations….Sample HCl evolution Variation

%CEI 20-37

mg/gREFERENCE 140HTLC 5 phr 125 -10,7

POSS 0,62 phr 130 -7,1HTLC 5 phr/POSS 0,62

phr 120-14,3

HTLC 5 phr theo 90 -36%HTLC 10 phr theo 40 -72%

modified HTLC 5 phrtheo 92,2

-34%modified HTLC 10 phr

theo 44,4-68%

modified HTLC 5 phr/POSS 0,62 phr theo ≅84

-40%modified HTLC 10

phr/POSS 0,62 phr theo ≅38-73%

18 TITLE


%CEI 20-37



phr 120-14,3




theo 44,4-68%




Optimisation of the dispersion can make the difference!!!!

19 TITLE


%CEI 20-37



phr 120-14,3




theo 44,4-68%




20 TITLE


%CEI 20-37



phr 120-14,3




theo 44,4-68%




These results must be consideredaside the improval of thermalbehaviour performances:

1. Chemical stability (higher Tonset)

2. Thermal decomposition shift

3. HCl evolution shift in temperature

SUMMING UP Despite a restricted number of papers in literature, a

comprehensive study of nanoadditives in PVC demonstrates their suitability for this matrix

Effects at nanoscale level are evident in features asthermal stability, degradation and HCl evolution

Stabilisation involves also the beginning of the degradation process (chemical effect on PVC matrix)

Amount involved can reach quantities lower than 0,5 phr

Synergistic effects can magnify the effects of nanoadditives

an platform

Thank you

Documents

Performance improvement and innovation: the role of ... · Performance improvement and innovation: the role of nanotechnologies. ... CEI 20-34/3-2. ... CEI 20-37. mg/g. REFERENCE