Analysis of the S-PVC gelation process

Analysis of the S-PVC gelation process:

determination of the degree of gelation using
DSC and ultrasound

J.P.D. Alves1, E. Hage Jr.1, A. Rodolfo Jr.2, R. Gonçalves3

1Federal University of São Carlos, Brazil; 2 Braskem S/A, Brazil; 3 State University of
Campinas, Brazil
Analysis of the S-PVC gelation process

Agenda

Overview of Braskem S/A

Overview of the NEO PVC Program

Analysis of the S-PVC gelation process: determination of the degree of gelation

using DSC and ultrasound
Analysis of the S-PVC gelation process

Agenda

Overview of Braskem S/A

Overview of the NEO PVC Program

Analysis of the S-PVC gelation process: determination of the degree of gelation

using DSC and ultrasound
 Analysis of the S-PVC gelation process
Braskem
Global Petrochemical Player

Gross Revenue Net Revenue EBITDA

US$ 12.3 bi US$ 9.7 bi US$ 1.6 bi

Exports Assets

US$ 2.3 bi US$ 11.7 bi

Note: Pro forma basis for 2007, with full consolidation of Ipiranga and Copesul.
Source: Braskem
 Analysis of the S-PVC gelation process

Large scale coupled with increased competitiveness

3rd largest producer of resins in the Americas

5,039
4,767 PVC
64
627
PP
3,250 * PE
1.230
2,906
515 2,728
760 135
4,348 3,537
1,210 2,152
1,355
725
1,975 2,593
685
971
670

Dow Exxon Braskem Formosa Equistar Chevron Nova Petroquímica

3rd 13th

2nd highest EBITDA margin in Global Petrochemical Industry

40%

30% Braskem
20%
17%
10%

0%
Sabic Reliance Nova Dow Westlake Georgia
Chemicals Gulf
* includes 160 k ton of PE from Petroquímica Triunfo
Source: Braskem – Companies info as of 2007 (Sabic as of 2006).
 Analysis of the S-PVC gelation process

Leadership in the Brazilian market

PE % PP %

32% 37%
52% 49%

16% 14%
OTHERS

IMPORTS
PVC % Resins %

27% 32%
54% 52%
19% 16%

Source: Braskem/Abiquim Dec 07

 Analysis of the S-PVC gelation process

Innovation and Technology as key value drivers

Over US$ 160 million

in R&D assets
200 researchers
8 pilot plants
187 patents filed
Focus on nanotechnology and intelligent
packaging
18% of resins sales derive from products launched
in the last three years
Partnership with universities and R&D centers in
Brazil and abroad

Source: Braskem
Analysis of the S-PVC gelation process

Agenda

Overview of Braskem S/A

Overview of the NEO PVC Program

Analysis of the S-PVC gelation process: determination of the degree of gelation

using DSC and ultrasound
Analysis of the S-PVC gelation process

NEO PVC – Concept (www.neopvc.com.br)

Núcleo de Estudos Orientados do PVC

PVC Oriented Studies Network, started 2005

NEO PVC is a mutidisciplinar network of researchers in the Academia and/or

R&D centers in Brazil

Coordinated by Braskem

Its action is planned, oriented and integrated to the company´s objectives

Its focus is on the generation and propagation of technologies for the

application of PVC

Braskem supports the project through the resources of its Vinyls Technology &
Innovation Center in São Paulo
Analysis of the S-PVC gelation process

NEO PVC – Objectives

Main:

Development of a culture of academic research on PVC technologies in Brazil

Generation of technological innovations
Reinforce Braskem´s position as a reference in the technology of PVC application
in Brazil
Analysis of the S-PVC gelation process

NEO PVC – Objectives

Main:

Development of a culture of academic research on PVC technologies in Brazil

Generation of technological innovations
Reinforce Braskem´s position as a reference in the technology of PVC application
in Brazil

Additional:

Development of specialized human resources for the PVC industry

Creation and diffusion of knowledge
Strenghtening of the relationship with the Academia and its members
Renovate PVC as a versatile, modern and environmentally safe material
 Analysis of the S-PVC gelation process

NEO PVC pipeline of research projects

Estimated date of conclusion

# Title Academia Main focus
S2/07 S1/08 S2/08 S1/09 S2/09 S1/10
1 PVC gelation assessment UFSCar Blends/composites
2 PVC/CPVC pipes for sprinklers USP Sustainability
3 PVC/glass fiber composites USP Blends/composites
4 In situ vulcanization of PVC/NBR blends UFSCar Blends/composites
5 Plastisol nanocomposites USP Nanocomposites
6 Plasticisation of PVC with biodegradable polymers UFSC Blends/composites
7 Biodegradable PVC compounds USF Blends/composites
8 Reinforcement of PVC with banana tree fibers Sociesc Blends/composites
9 Reinforcement of PVC with glass fibers UFSCar Blends/composites
10 Preparation of Brazilian organoclays UFSCar Nanocomposites
11 Carbon nanotube nanocomposites UFSC Nanocomposites
12 Low smoke PVC compounds UNICAMP Nanocomposites
13 PVC gelation assessment with ultrassound UFSCar Blends/composites
14 In situ vulcanization of PVC/NBR blends – scale up UFSCar Blends/composites
Analysis of the S-PVC gelation process

Agenda

Overview of Braskem S/A

Overview of the NEO PVC Program

Analysis of the S-PVC gelation process: determination of the degree of gelation

using DSC and ultrasound
Analysis of the S-PVC gelation process

Objectives of the project

Master degree dissertation presented in December 2007 by Juliana Alves in the

Federal University of São Carlos – Materials Enginnering Department

Main objectives:

– Comprehension and study of the PVC gelation process

– Quantify the degree of gelation using differential scanning calorimetry,

understanding this technique

As a consequence of the main objectives, evaluate ultrassound analysis as na

alternative method for the evaluation of the degree of gelation of PVC compounds
 Analysis of the S-PVC gelation process

Background

During the processing S-PVC resins or

compounds gelates/fuses when heated
and sheared

Operation conditions and thermo-

mechanical environment during
processing modifies the initial granular
particles

The identity of the grains, primary particles

and primary crystals is destroyed during
gelation and fusion

After fusion and cooling secondary

crystallinity is formed

MARQUES, P.R.; COVAS, J.A. Processing characteristics of U-PVC compounds Companhia. Ind. de Resinas Sintéticas, Cires, S.A. 2003.
 Analysis of the S-PVC gelation process

Backgound

Allsopp (1982):

The breakdown of PVC grains can only occur at the aggregates or primary particles level,
whenever the material is subjected to very high shear stress, as it is the case with torque
rheometers.

In typical industrial equipment, the fusion mechanism involves Compaction, Densification,

Fusion and Elongation of the PVC grains (CDFE mechanism), which means that:

– the main "flow unit" is the PVC grain

– initially, PVC grains are compacted and densified and their internal porosity is
progressively eliminated as pressure and temperature rise, initiating an intra-granular
fusion process

– Marques; Covas (2003) identified grain boundaries over a significant distance along the
screws of an extruder

– Intragranular fusion and shear stress causes elongation in the flow direction

ALLSOPP, M.W. Mechanism of Gelation of Rigid PVC during Processing. Imperial Chemical Industries Limited, 1982.
MARQUES, P.R.; COVAS, J.A. Processing characteristics of U-PVC compounds Companhia. Ind. de Resinas Sintéticas, Cires, S.A. 2003.
 Analysis of the S-PVC gelation process

Background

ALLSOPP, M.W. Mechanism of Gelation of Rigid PVC during Processing. Imperial Chemical Industries Limited, 1982.
MARQUES, P.R.; COVAS, J.A. Processing characteristics of U-PVC compounds Companhia. Ind. de Resinas Sintéticas, Cires, S.A. 2003.
Analysis of the S-PVC gelation process

Background

MARQUES, P.R.; COVAS, J.A. Processing characteristics of U-PVC compounds

Companhia. Ind. de Resinas Sintéticas, Cires, S.A. 2003.
 Analysis of the S-PVC gelation process

Background

Summers model:

After cooling the secondary crystallininty

Primary particles original morphology is formed

Primary particles partially gelled, showing

the interdiffusion of the polymer chains

SUMMERS, J. Journal of Vinyl and Additive Technology, 3, 130, 1997.

FILLOT, L..A., et al. Journal of Vinyl and Additive Technology, 12, 98, 2006.
 Analysis of the S-PVC gelation process

Background

Assessment of PVC degree of gelation - DSC

GILBERT, M.; VYVODA, J.C. Polymer, 22, 1134, 1981.

 Analysis of the S-PVC gelation process

Background

Assessment of PVC degree of gelation – Cappilary rheometry

ALVES, J. P. D.; RODOLFO JR., A. Polímeros, 16, 2006.

Analysis of the S-PVC gelation process

Background

Assessment of PVC degree of gelation – Dichloromethane (EN 580) or acetone

(ASTM D2152) immersion test
Analysis of the S-PVC gelation process

Project

First part:

Understand the gelation process

Analise the morphological changes during the gellation/fusion process through

torque rheometry and scanning electron microscopy

Assess the degree of gelation through DSC

Analysis of the S-PVC gelation process

Project

Second part:

Correlate acoustic properties (ultrassound) and degree of gelation assessed by

DSC on PVC pipe samples taken from a customer

Correlate mechanical properties obtained by acoustic methods (ultrassound) and

conventional (tensile) methods
Analysis of the S-PVC gelation process

Experimental –Part 1

Ingredient Ratio (pcr) Function of formulation

Norvic® SP 767 P 100 Suspension PVC Resin

Naftosafe® CZ 3035 2,8 Ca/Zn-based thermal stabilizer

Barralev® C 10 Calcium carbonate

Calcium stearate 1 Internal lubricant

Analysis of the S-PVC gelation process

Results – Part 1
Analysis of the S-PVC gelation process

Results – Part 1
Analysis of the S-PVC gelation process

Results – Part 1
Analysis of the S-PVC gelation process

Results – Part 1
Analysis of the S-PVC gelation process

Results – Part 1
Analysis of the S-PVC gelation process

Results – Part 1
Analysis of the S-PVC gelation process

Results – Part 1

Test temperature (oC) DSC degree of gelation

170 52,5%

180 54,3%

190 67,4%
Analysis of the S-PVC gelation process

Experimental – Part 2

External diameter
Pipe sample Mass temperature (oC)
(mm)

1 60 192

2 60 199

3 110 195

4 110 191

Taken from a customer during machine setup

 Analysis of the S-PVC gelation process

Experimental – Part 2

Ultrassound generator

Recepting transducer
Emmiting transducer

Pipe sampe

E= Elastic modulus
ρ = Density
V = Velocity of propagation of the ultrassound wave
Analysis of the S-PVC gelation process

Results – Part 2

Elastic modulus
DSC degree Mass Shear modulus
Pipe sample (ultrassound)
of gelation temperature (oC) (ultrassound) (MPa)
(MPa)

1 48% 192 4.766 1.783

2 57% 199 4.816 1.810

3 52% 195 4.698 1.676

4 48% 191 4.625 1.645

Analysis of the S-PVC gelation process

Results – Part 2

4.850
Ultrassound elastic modulus (MPa)

R2 = 0,4547

4.800

4.750

4.700

4.650

4.600
46% 48% 50% 52% 54% 56% 58%
DSC degree of gelation (%)
Analysis of the S-PVC gelation process

Results – Part 2

Elastic modulus
Elastic modulus
Pipe sample DSC degree of gelation (ultrassound)
(tensile) (MPa)
(MPa)

1 48 2.575 4.766

2 57 2.902 4.816

3 52 3.318 4.698

4 48 3.082 4.625
Analysis of the S-PVC gelation process

Conclusions

It was possible to monitor the morphological changes as well as to characterize the

behavior of gelation and fusion

Through DSC tests it was possible to obtain the degree of gelation of samples
processed by Torque Rheometry at different testing temperatures, keeping a
constant rotation. It is concluded that the processing temperature is closely linked
to the degree of gelation

The degree of gelation is correlated to the elastic and shear modulus obtained by
ultrasound – apparently, the higher the degree of gelation, the greater the value of
the modulus

Ultrasound seems to be a feasible technique to be further evaluated in order to be

used to correlate the acoustic properties of the suspension PVC compounds with
their degrees of gelation
Analysis of the S-PVC gelation process

Future work and perspectives

Evaluate different types of transducers (longitudinal and transversal) and its

influence on frequency and velocity of propagation

Analise the influence of the formulation components on the velocity and modulus
by ultrassound

Correlate DCMT x DSC x ultrassound measurements of the degree of gelation on

samples produced in a torque rheometer

Develop ultrassound equipments for the on-line measurement of the degree of

gelation
Analysis of the S-PVC gelation process

Thank you for your attention!

Have a safe and pleasant trip back home!
antonio.rodolfo@braskem.com.br

www.neopvc.com.br