RECYCLING OF GLASS FIBER COMPOSITES

This thesis comprises 30 ECTS credits and is a compulsory part in the Master of Science with a Major in resource recovery – sustainable engineering 120 ECTS credits

No. 7/2011

RECYCLING OF GLASS FIBER COMPOSITES

By

RAMESH KRISHNAMOORTHI

ZHANG SHIZHAO

ii

This thesis was done as a part of the research project, “Recycling of waste glass fiber

reinforced plastic with microwave pyrolysis”.

This research and development project, financed by the EU Commission, is aiming to find a

solution for recycling glass fiber reinforced plastics and accordingly decrease the amount of

plastic waste ending up on landfills. Stena Metall AB is the coordinating beneficiary. The

associated beneficiaries are Stena Sp z o o, Gisip AB, University College Borås and

University of Economics in Poznan.

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RECYCLING OF GLASS FIBER COMPOSITES

Authors:

Ramesh Krishnamoorthi, [email protected]

Zhang Shizhao, [email protected]

Master thesis

Subject Category: Polymer technology ,recycling, glass composite fibres

University College of Borås School of Engineering SE-501 90 BORÅS Telephone +46 033 435 4640

Examiner: Professor Mikael Skrifvars

Supervisor : Dan Åkesson

Supervisor,address: University of Borås, School of Engineering

501 90, Borås

Date: June 2011

Keywords: Polypropylene (PP), Maleic Anhydride Modifie Polypropylene(MAPP), Grinded and microwave pyrolyse composites (MGC), Grinded composites (GC), Neoxil, Virgin glass fiber,CaCO3, Hammer mill fiber, micro-compounder, injection, Termogravimetric Analysis (TGA), Tensile Testing, GCMSAnalysis, Dynamic Mechanical Analysis (DMA), MicrowavePyrolysis, Different Scanning Calorimetry(DSC), Distillation, Polymer oil

mailto:[email protected]

mailto:[email protected]

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ACKNOWLEDEMENT

We would like to owe our sincere gratitude to our supervisor Dan Åkesson, who supported us

and guided throughout this project .This work would not have been possible without him, he

was the one who assisted us in numerous ways and We have to mention this he is one good

person, who has a lot of patience in handling and teaching students.

We thank our examiner Professor Mikael Skrifvars, University of Boras, we would not have

got an opportunity to work in this project without his support and knowledge. His advice and

mentoring helped us a lot throughout our work.

In our daily work, We have been blessed with a friendly and cheerful lab assistant Haike

Hilke , She was the one who helped us and sourced us a quality work station with which

much of the work had been done on. I would also like to thank Adib kalantar mehrjerdi, for

his help in clearing our doubts and proceed with our experiments.

It would have been incomplete if we have forgot to thank Stena metal AB, they were helping

us in providing materials for our work.

Our final words go to our family, who supported us continuously throughout our studies. We

want to thank my family, whose love and guidance is always with me in whatever we pursue.

Without their encouragement and support, it would be definitely hard for us to finish this

degree.

Regards

Ramesh krishnamoorthi

Zhang Shizhao

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ABSTRACT

Composites are the materials which can be used for a wide variety of applications and

products such as sports equipment, aerospace and marine because of light and stiffness

properties. Composites are often made from thermoset resin with glass fibers.

In this study, two ways of recycling composites were evaluated, which are microwave

pyrolysed composites (MGC) and mechanical composites (GC). These glass fibers were

going to be compounded with Polypropylene (PP) or Maleic Anhydride Modified

Polypropylene (MAPP) and then injection moulded the sample by Micro-compounder.

In order to get better adhesion to the polymer, a coating was added. The Neoxil 5682-

polypropylene water emulsion was evaluated.

The samples were characterized by Tensile Testing, Thermogravimetric Analysis (TGA),

Different Scanning Calorimetry (DSC), and Dynamic Mechanical Analysis (DMA) to find a

optimum combination of recycled glass fiber reinforced polymer.

Microwave pyrolysis is a new research area. The glass fiber, polymer oil and gas can be

obtained by heating the composite with microwaves to in an inert atmosphere. The polymer

oil can be distillated and then evaluated with GC-MS; in order to obtain the chemical

compositions.

Keywords: Composites, grinded and microwave pyrolyse composites (MGC), grinded

composites (GC), Polypropylene (PP), Maleic Anhydride Modified Polypropylene (MAPP),

Micro-compounder, Tensile Testing, Thermogravimetric Analysis (TGA), Different Scanning

Calorimetry (DSC), and Dynamic Mechanical Analysis (DMA), Microwave pyrolysis,

polymer oil, distillation, GCMS Analysis.

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ABBREVIATION

TGA Thermogravimetric Analysis

DSC Different Scanning Calorimetry

DMTA Dynamic Mechanical Thermal Analysis

GC-MS Gas Chromatography Mass Spectrometry

PP Polypropylene

MAPP Maleic Anhydride Modifie Polypropylene

MGC Microwave pyrolysed glass composite(knife milled)

GC Grinded composite(Mechanical recycling)

NGMGC Non grinded microwave pyrolysed glass composite

NGMGCCR Non grinded microwave pyrolysed glass char removed composite

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CONTENTS1. INTRODUCTION ............................................................................................................ 1

1.1 OLD RECYLING METHODS ...................................................................................... 1

1.2 MICROWAVE PYROLYSIS .......................................................................................... 2

2. MATERIALS AND METHODS ..................................................................................... 3

2.1 MATERIALS ................................................................................................................. 3

2.1.1 VIRGIN GLASS FIBERS .................................................................................. 3

2.1.2 MICRO WAVE PYROLYSED GLASS FIBERS .............................................. 3

2.1.3 GRINDED GLASS COMPOSITES ................................................................... 4

2.1.4 CALCIUM CARBONATE ................................................................................. 4

2.1.5 POLYPROPYLENE ........................................................................................... 5

2.1.6 MALEIC ANHYDRIDE MODIFIED POLYPROPYLENE ............................. 5

2.2 MATERIAL TREATING METHODS ............................................................................ 6

2.2.1 GRINDING METHODS OF GLASS FIBERS .................................................. 6

2.2.2 CHAR REMOVED GLASS FIBERS ................................................................ 7

2.2.3 COATING OF GLASS COMPOSITE FIBER ................................................... 7

2.2.4 COMPOSITION ................................................................................................. 8

2.3 METHODS OF PREPARATION AND CHARACTERIZATION .................................. 8

2.3.1 TWIN SCREW MICRO COMPOUNDER ........................................................ 8

2.3.2 DYNAMIC MECHANICAL THERMAL ANALYSIS ................................... 10

2.3.3 DIFFERENTIAL SCANNING CALORIMETRY ........................................... 11

2.3.4 THERMAL GRAVIMETRIC ANALYSIS ...................................................... 13

2.3.5 FLEXURAL TEST ........................................................................................... 14

2.3.6 TENSILE TEST ................................................................................................ 16

2.3.7 GAS CHROMATOGRAPHY MASS SPECTROMETRY (GC-MS) ............. 17

3. RESULTS AND DISCUSSION ..................................................................................... 18

3.1 THERMOGRAVIMETRIC ANALYSIS RESULTS ...................................................... 18

3.2 DIFFERENTAIL SCANNING CALRIMERTY RESULTS .......................................... 21

3.3 DMTA RESULTS. ....................................................................................................... 23

3.4 FLEXURAL RESULTS ............................................................................................... 25

3.5 TENSILE RESULT ANALYSIS ................................................................................... 31

3.6 SUMMARIZATION OF RESULTS ............................................................................. 37

3.7 FRACTIONAL DISTILLATION OF OIL .................................................................... 38

4. CONCLUSION ............................................................................................................... 41

5. REFERENCE ................................................................................................................. 42

6. APPENDIX ..................................................................................................................... 44

1

1. INTRODUCTION

Glass fiber composite is a composite made of polymer reinforced with fiber made of glass.

Glass fiber composites are widely used in many industries including windmill, automotives,

insulation for building, marines, construction material and external door skins due to their

combination of properties, strength, durability, high strength, less weight, heat resistance and

corrosion resistance. Glass fiber composite are hard to recycle especially those which are

produced from thermosetting plastic. Thermosetting plastics or resins are crosslinked

polymer. This can be achieved heating the material or by irradiation. After fully cured the

material cannot be reformed or remolded in to another shape [1]. Because of this high

characterization glass fiber composite are used in manufacturing of windmill blades. Global

energy needs increase growth rate of wind turbines, both in terms of numbers and sizes of

turbines. The size of modern turbines is 100 times bigger than those in 1980. As the size of

turbine increase, the usage of the material also increases. For each one kilowatt requires 10

kg of rotor blade material. The average life span of windmill is around 20 – 25 years It is

predicted that, from the year 2040 380,000, tonnes of fiber composites will be disposed each

year [2]. The methods which are available to treat the discarded wind mill blades are not

feasible.

1.1 OLD RECYLING METHODS

The available ways of treating the dismantled wind mill blades are landfill, incineration and

material recycling. Landfill is not a feasible of treating waste as it is banned in most of the

European countries. The next common method is incineration, which is called as combined

heat and power plant. The heat from incineration can be used to produce electricity and in

district heating system. But 60% of material ends up in ashes after incineration. This ash may

be pollutant due to presence of inorganic substances in composites and after post treatment it

can be land filled or used as filler for construction material. This may also lead to releasing of

harmful gases in the environment because of inorganic contents. Pre-treatment methods of

windmill blades are also a strain to the environment in terms of energy used. This working

environment is harmful for the health and safety of the workers. The available recycling

methods for glass fiber composites are mechanical recycling, chemical recycling, and thermal

recycling. In the mechanical recycling, windmill blades are fed in to mechanical shredder and

the materials are slammed with hammer until the resins are removed from bonding. In these

methods only 30% of the material used can be recovered to form new Glass fiber composite.

[3].Due to the presence of filler

Chemical recycling, in this method of recycling c

fibers. This method requires high capitation and has potential hazards to the environment

Pyrolysis is one of the methods in thermal recycling, in this method the waste material is

thermally treated in inert atmosphere to degrade the polymer into oil and gas. But the

recovered fiber looses much of its strength due to thermal stress

fuel and refined to feedstock chemicals. But it has some defects like chemical recycling. All

these methods have defects to implement in commercial ways.

So they are recycled using a new method called micro wave pyrolysis to treat the waste.

Microwave pyrolysis is a new research area for treating glass composite fiber. In this process,

the composite is treated with microwaves, which separate fiber strands by degrading polymer

into oil and gas. The glass fibers can thereby be reused for the preparation of new

composites.

1.2 MICROWAVE PYROLYSIS

Figure 1: Process flow diagram of Microwave Pyrolsis

Microwave pyrolysis is a thermal process in which conversion of organic compounds takes

place during heating by microwaves

windmill blades are heated with micro waves to 400 to 600 °

to separate glass fibers and polymers as oil

than other heating methods. It requires only shorter heating time

less important in microwave heating. So it requires less processing a

2

presence of fillers, it remains hard to manufacture in to another product.

Chemical recycling, in this method of recycling chemicals are used to remove resin from the

fibers. This method requires high capitation and has potential hazards to the environment


atmosphere to degrade the polymer into oil and gas. But the

recovered fiber looses much of its strength due to thermal stress [4]. The oil can be used as


thods have defects to implement in commercial ways.



eated with microwaves, which separate fiber strands by degrading polymer


MICROWAVE PYROLYSIS

: Process flow diagram of Microwave Pyrolsis

pyrolysis is a thermal process in which conversion of organic compounds takes

by microwaves in inert environment. In this process the discarded

windmill blades are heated with micro waves to 400 to 600 °-C without presence of oxygen

separate glass fibers and polymers as oil [5]. Microwaves can heat objects more uniformly

than other heating methods. It requires only shorter heating time[6]. The size of the object is

less important in microwave heating. So it requires less processing and pre

remains hard to manufacture in to another product.

hemicals are used to remove resin from the

fibers. This method requires high capitation and has potential hazards to the environment [3].


atmosphere to degrade the polymer into oil and gas. But the

. The oil can be used as




eated with microwaves, which separate fiber strands by degrading polymer


: Process flow diagram of Microwave Pyrolsis

pyrolysis is a thermal process in which conversion of organic compounds takes

in inert environment. In this process the discarded

C without presence of oxygen

. Microwaves can heat objects more uniformly

. The size of the object is

nd pre- processing cost.

3

Microwave pyrolysis produces less gaseous amount from 5 to 20 percent when compared to

other recycling methods [7]. The product yield is very high compared with other recovery

process. The figure 1 shows the process flow diagram of the micro wave pyrolysis.

2. MATERIALS AND METHODS

2.1 MATERIALS

2.1.1 VIRGIN GLASS FIBERS

Glass fibers are made from extrusion of silica. It is a material formed from very fine strands

of glass. The silica can be heated and drew in to fine strands of fibers. The glass fibers are

mixed with polypropylene and made in to pellets for this project. Virgin glass fiber is used as

a reference to be compare with other material. Virgin glass fibers was already blended in the

standard composition and made in to beads and they were shown in the figure 2. These were

received from poly kemi,sweden.

Figure 2: Virgin glass fiber composites

2.1.2 MICRO WAVE PYROLYSED GLASS FIBERS

The glass fiber composite were treated with microwave pyrolysis method and the glass

strands and polymer was separated. The glass fibers were received from Stena Metal AB. The

sample of microwave pyrolysed glass fiber was shown in the figure 3.

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Figure 3: Microwave pyrolysed glass fiber

2.1.3 GRINDED GLASS COMPOSITES

The grinded glass composites are acquired from the process called mechanical recycling. In

this method the wind mill is feed in to mechanical shredder and broken down into small

pieces and hammered until the resin worn off from the glass fiber strands. The sample of

grinded glass composite was shown in the figure 4.

Figure 4: Sample of Grinded glass composite

2.1.4 CALCIUM CARBONATE

Calcium carbonate is chemical compound available in the earth crust and found throughout

the world. The chemical formula is CaCO3. The most common forms of calcium carbonate

are chalk, limestone and marble are produced by sedimentation of shells of snails, shellfish

and coral over million years. It is prepared by calcining crude calcium oxide. Then water is

added to form calcium hydroxide, and it is precipitate by passing CO2 through this solution

to produce calcium carbonate [8]. It is used as filler in manufacturing of polymers. Calcium

carbonate is used as reference. The sample of CaCO3 is shown in figure 5.

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Figure 5: The chemical structural and sample of CaCO3 [9]

2.1.5 POLYPROPYLENE

Polypropylene is a thermoplastic resin by propylene polymerization. The abbreviation is PP.

It was first produced by Giulio Natta in 1954 and was commercialized in 1957. As the major

thermoplastic, it is growing fast in the commercial business. In the area of plastic, it has a

wide range of applications based on economic condition, mechanical properties, easier

machining and other aspects. PP is a preferred material in the many application fields [10].

Figure 6: Chemical structural and sample of Polypropylene (PP)

The formula of Polypropylene is [C3H6] n. usually, as a translucent solid which is Non- toxic,

tasteless, small density (the density of shock resistance of Polypropylene < 1), the strength,

and stiffness, hardness and heat- resistance is better than polyethylene. PP can be used around

100 degree [11]. And it also has good performance of electrical, high frequency insulation.

2.1.6 MALEIC ANHYDRIDE MODIFIED POLYPROPYLENE

The chemical formula and sample of Maleic anhydride is shown in Figure 7. The melting

point is 52.8 ℃ [12]. Method of grafting maleic anhydride on a Polypropylene is a

simple process. The anhydride is made to react with polypropylene in the

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heterogeneous phase and in the presence of dilaurylperoxide as radical initiator. The

process has to be carried out in inert condition under nitrogen pressure at temperature

progressively rising to 110° c, for time period of .5 to 3 hours [13]. The MAPP was received

from VEOH GMBH in Germany.

Figure 7: Chemical structure and sample of Maleic anhydride modified Polypropylene

2.2 MATERIAL TREATING METHODS

The materials were treated with different methods before extruded in the micro compounder.

These methods are followed to improve the blending of fibers and resins. The numerous

compositions of the glass fibers and polypropylene are also used.

2.2.1 GRINDING METHODS OF GLASS FIBERS

Figure 8: Microwave pyrolysed glass composite (left) knife and (right)Hammer milled

The microwave pyrolysed glass fibers are grinded by three methods before feeding in to

micro compounder. The recycled glass fibers received from the Stena metal AB are a grinded

before microwave pyrolysis. Non-Grinded, Knife milled and Hammer milled (Denmark) are

the three grinding methods. The hammer milled fibers were grinded by Stena metal,

Denmark. The Knife milled fibers was done by knife milling machine in university of Boras.

The sample of knife and hammer milled glass fibers are shown in figure 8.

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2.2.2 CHAR REMOVED GLASS FIBERS

The recycled glass fibers are treated in the furnace with a capacity of 300° c to 3000°c. The

glass fiber is heated up to temperature of 500° c for 40 minutes to remove char. The glass

fibers are weighted before and after the heat treatment. The weight is reduced up to 97%. The

sample of char removed glass fiber was shown in figure 9.

Figure 9: Char removed glass composite

2.2.3 COATING OF GLASS COMPOSITE FIBER

Neoxil is used as sizing material in this project. The ratio of water mixed with neoxil is 1:6

ratios. The allowed weight increase of the product is 0.25% to 0.5%.The fibers were heated

up to a temperature of 80°C to remove moisture. Then glass fibers were spread in a sheet and

sprayed with diluted neoxil. The coated fibers heated again in the furnace in the temperature

of 60 °C for 40 minutes. The weight of the sample is measured in each step. Again the fibers

were coated and heated under same conditions. The fibers are kept in room temperature for

10 to 14 hours to check if the weight of the fibers remains same. The samples which were

coated are:

• Non grinded microwave pyrolysed glass fiber

• grinded microwave pyrolysed glass fiber

• Non grinded microwave pyrolysed glass fiber without char

• Grinded glass composite(Mechanically recycled)

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2.2.4 COMPOSITION

The composition of the mixing of glass fiber, polypropylene and Maleic anhydride

polypropylenes are

• 30% of glass fibers and 70% of PP

• 30% of glass fibers and 70% polymer(90% of PP and 10% of MAPP)



2.3 METHODS OF PREPARATION AND CHARACTERIZATION

2.3.1 TWIN SCREW MICRO COMPOUNDER

Micro compounder is a unique material compounding machine used in a laboratory scale.

The compounder used in our laboratory is a twin screw micro compounder with a capacity of

15ml.It helps in developing new type of material compounds in a laboratory scale. The micro

compounder consists of two detachable conical mixing screws in a fluid tight compartment.

The housing and the conical screws are specially treated to minimize wear and make them

resistant against chemicals. It consists of six separate heating zones which allow having a

precise control over the processing temperature. The maximum working temperature of the

micro compounder is 450° C and screw can work at a speed of 250 RPM. Argon gas is used

during compounding to prevent agglomeration. The working parameter of micro compounder

are processing temperature at six heating zones are 210° C and the screw is maintained at a

speed of 80 RPM. The polymers and glass fibers can be filled into twin screw micro-

compounder via a recycle barrel. The viscous material can flow out from an opening at the

bottom of the housing. An injection molding machine is used to inject the viscous

compounded materials into a mold which is controlled by a specific temperature and pressure

[14]. The parameter used in injection moulding machine are listed in the table 1. The xplore

twin screw micro compounder and injection moulding machine were shown in the figure 10.

The test sample prepared was shown in the figure 11.

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Table 1: Parameters of injection moulding machine

Heating temperature (Injector) 198 ℃

Heating temperature (Mould) 80 ℃

Pressure

10bar (2secs.)

16bar (5secs.)

16bar (8secs.)

Figure10: Twin screw micro compounder (left) and injection moulding machine (right)

Figure11: Test samples

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2.3.2 DYNAMIC MECHANICAL THERMAL ANALYSIS

Dynamic Mechanical Thermal Analysis is otherwise known as DMTA or DMA is versatile

thermal analysis method. It provides information about samples thermo dynamic properties.

The DMA applies oscillating force to the sample to record the temperature-dependent visco-

elastic properties and determines the modulus of elasticity and the damping values. Storage

modulus reflects stiffness, loss modulus and tan delta mainly reflect the damping

characteristic (energy dissipation). The glass transition temperature Tg can be measured by

the onset point, by the loss modulus peak, by the tan delta peak.

The DMA Q800 was used in the research. The Q800 DMTA works over a wide temperature

range from -150 ℃ to 600 and the test configurations were Three-point bending, single and

dual cantilever, shear, compression, and tension. Liquid Nitrogen is used to equilibrate the

temperature to - 60°C [15, 16]. The figure 12 shows the DMTA instrument and figure 13

shows the dimension of the sample. The specifications were listed in the table 2.

Figure12: Dynamic mechanical thermal analysis instrument

Figure13: Sample dimension

31.2mm

9.9mm

4.05mm

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Specification:

Table 2: Temperature Ramp / Frequency Sweep parameters

Type of Experiment Temperature Ramp / Frequency Sweep

Test Configuration Single Cantilever

Amplitude 15.0000 (um)

Equilibrate temperature -60.00℃

Final temperature 140 ℃

Ramp rate 2.00℃ /min

Frequency 1.00 Hz

2.3.3 DIFFERENTIAL SCANNING CALORIMETRY

Differential scanning calorimetry stands for the abbreviation DSC and is shown in the figure

14. DSC is used to analyze temperature and heat flow associated with thermal transition in a

material. A precisely definition of Differential Scanning Calorimetry is the measurement of

the change of difference in the heat flow rate to the sample and to a reference sample while

they are heated in a controlled temperature.DSC techniques measure properties like include

glass transitions, "cold" crystallization, phase changes, melting, crystallization, product

stability, cure / cure kinetics, and oxidative stability [17].

Figure 14: Differential scanning calorimetry

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Sample preparation

During the experiment, a sample of 5-10 mg was used to get a better resolution and minimize

temperature gradients inside the sample. The samples are fixed in a small aluminum pan to

provide better thermal conductance to the sample and to prevent from material pillage [18].

Figure 16: DSC Press (left) and Aluminum Pans and Lids (right)

Method

The basic method includes three cycles which are heating, cooling and heating. Mass flow

can be controlled by setting, it includes that nitrogen as the gas and flow rate is 50 ml / min.

Table 3: Parameters of DSC method

Cycle Temperature Range Speed Isothermal

Heating (1) Ambient T~-60 ℃~220 ℃ 10 ℃ / min 1.00 min

Cooling 220 ℃~ -60 ℃ 20 ℃ / min 1.00 min

Heating (2) -60 ℃~220 ℃ 10 ℃ / min 2.00 min

The glass transition temperature (Tg), crystallization temperature (Tc) and melting point can

be obtained from DSC curves.

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2.3.4 THERMAL GRAVIMETRIC ANALYSIS

Thermo gravimetric analysis (TGA) was TGA was used to analyze the thermal stability of a

material. It was shown in the figure 15. TGA provides measurement of mass change in

materials with transition and thermal degradation. In generally, TGA was an excellent chose

to determine characteristics of polymers, decomposition point of explosive, and determine the

degradation temperature.

The objective of the study was to analysis the change in the weight of sample as a function of

time or temperature in a controlled temperature program in a controlled environment. During

analysis the result, the thermal stability and components of the sample can be studied. TGA

Q500 (TA Instrument) was used for this analysis. Small sample which was around 10 mg was

used. A standard Platinum pan was given for testing the sample. The TGA was always

purging with gas like nitrogen and oxygen the changing weight along with temperature and

time can be saved and plotted [19].

Figure 15: Thermogravimetric analysis (Q500)

Method

Conventional TGA was the best choice for this case. Sample was heated at a constant rate,

and can be determined thermal stability and composition. The type of experiment was TGA

ramp which was the process of increasing temperature, or TGA ram with gas switch which

can switch from an inert to another gas (for example: switch from Nitrogen to Oxygen).

The original materials (GC, MGC and Neat PP) are heating to 210℃ and using 20℃ / min.

The isothermal for 20.00 min; and only Nitrogen as the mass flow control setting.

For the testing samples, it needs to change another method to prove the weight changing

during heating by TGA.

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Table 4: Parameters of TGA method

Temperature Speed Gas

Ambient T – 600 ℃ 20 ℃ / min Nitrogen

600 ℃- 800 ℃ 20 ℃ / min Oxygen

2.3.5 FLEXURAL TEST

Flexural testing was a reliability testing for production under 3-point Bending condition. The

testing sample must be quite flexible, such as wood, composites and polymers. It measures

the force required to bend simple beam loading [20].

Figure 17: Tinius Olsen H10K-T UTM (left) and sample specimen (right)

Flexural testing was a reliability testing for production under 3-point Bending condition. The

testing sample must be quite flexible, such as wood, composites and polymers. It measures

the force required to bend simple beam loading.

The flexure test was used to know the flexure strength, elongation, and flexure modulus. The

test was based on ISO 14125 standard using a Tinius Olsen H10K-T UTM (universal testing

machine) shown in figure 17 (left) and Q Mat. It needs to choose the optimal method or

specification which was depending on different testing samples. In order to get an optimum

result, 5 specimens should be tested for each sample group. The table 5 represents the

specification of flexural test.

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Table 5: Specification of flexural test

Load range 500 N

Displacement range 20 mm

Test speed 10 mm/min

Span 64 mm

Strain 10%

Approach 0.5 mm/min

preload 8 N

Auto return on

The Flexure Stress (σf ) and Flexure Modulus (Ef ) can be calculated by these formulas:

σf = (3PL / 2bd2)

Ef = (L3m / 4bd3)

P – Load at a given point on the load deflection curve, (N)

L – Support span, (mm)

b – Width of test beam, (mm)

d – Depth of tested beam, (mm)

m – Gradient of the initial straight-line portion of the load deflection curve, (P/D), (mm)

D – Maximum deflection of the center of the beam (mm)

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2.3.6 TENSILE TEST

Tensile testing was a method to determine tensile strength, failure strain, and tensile modulus

of glass fiber reinforced polymer. It also can measure extent to elongate to the breaking point.

The testing sample was installed in a specified grip separation, and performed on a Tinius

Olsen H10K-T UTM (universal testing machine) shown in the figure 17(left) and Q Mat

software. Five samples were tested in each batch to get an optimum result. [21]. The figure

represents type of sample used and paramenter of the tensile test is listed in table 6.

Figure 18: Tensile Test Specimen

Table 6: Specification of tensile test

Load range 5000 N

Extension range 100 mm

Gauge length 24.8 mm

Test speed 20 mm/min

Approach 20 mm/min

preload 0 N

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2.3.7 GAS CHROMATOGRAPHY MASS SPECTROMETRY (GC-MS)

Gas Chromatography Mass Spectrometry was a testing method to identification and

quantization of volatile and semivolatile organic compounds in complex chemical mixtures.

It determines the molecular weights and elemental compositions of unknown organic

sample.[22] The pyrolysis oil was tested in this equipment. The spectrum results can present

different types of chemical compositions which are existing in a pyrolysis oil, such as

Toluene, Benzen, Alpha-methylstyrene. For example, styrene can be recovered on an

industrial basis. Figure 19 shows the GC-MS. The table 7 lists the parametrs of GC-MS.

Figure 19: GC-MS

Table 7: Parameters of GC-MS

Inlet temperature 135 ℃

Detector temperature 270 ℃

Level

Rate 12

Final temperature 210 ℃

Time 16.75 mins

Carrier flow parameters Column

Length 30 mm

Diameter 0.25 mm

Gas Helium

Flow 1.0

ml/min

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3. RESULTS AND DISCUSSION

The compounded microwave pyrolysed glass fibers reinforced with polypropylene and

Maleic anhydride polypropylene were subjected to thermal and mechanical analysis. The

results for all the combination were tabulated and discussed.

3.1 THERMOGRAVIMETRIC ANALYSIS RESULTS

The thermogravimetric analysis was used to measure the mass of sample which was heated in

a constant rate at a controlled atmosphere. The TGA curve mostly displays weight losses. In

each batches a samples of 5 to 15 mg was analyzed to measure the mass change and

decomposition temperature. The temperature used to compound composites was 210°C. So

the materials PP, MGC and GC were analyzed up to temperature 210°C.

Figure 20: Thermogravimetric analysis graph for MGC (Left) and GC (right) at (210°C)

The TGA graph for MGC and GC at (210°C) shown in figure 20. The respective residue of

MGC and GC was 99.87%, 97.49% from 100%. There was no significant change in weight.

The weight loss percentage in GC was much higher than MGC in this temperature because of

presence of filler due to mechanical grinding. Thus, it can prove that the temperature was

suitable for manufacturing composites.

Comparison of PP, MGC (800℃) and MGC reinforced PP shown in figure 21. On heating up

to 550℃ by controlled nitrogen, the weight of neat PP became 0, further by heating up until

600℃, the net PP completely disappeared. On comparing the net PP curve with MGC

reinforced PP curve, after 600℃, only the MGC fiber was left. Between 600℃ and 800℃, it

should change the controlled gas to oxygen. The weight of MGC was declining in the MGC

curve.

19

Figure 21: Comparison of PP, MGC (800℃) and MGC reinforced PP

Finally, the residue of MGC was 96.13% from 100%.Compare with 30% MGC fiber in

composites, the weight was declining to 26.81%. So, the declining value was almost the

same.

Figure 22: Comparison of MGC reinforced PP and CaCO3 reinforced PP

Comparison of MGC reinforced PP and CaCO3 reinforced PP shown in figure 22. MGC

reinforced with There was no significant change in declining percentage of polymer lost.

But, the residue of MGC reinforced PP was much higher than CaCO3 reinforced PP.

20

Figure 23: Comparison of 40% NGMGC reinforced polymer (90%PP and 10%MAPP) and

NG MGC reinforced polymer (90%PP and 10%MAPP)

Comparison of 40 % NGMGC and NGMGC reinforced with polymer (90% PP and 10%

MAPP) in figure 23. There was no significant change in declining percentage of polymer lost.

But, the residue of 40% NG-MGC reinforced polymer was much higher than another residue

value. Because it contains more fibers in the composite which improves mechanical

properties

Figure 24: Comparison of MGC reinforced PP and GC reinforced PP

Comparison of MGC and GC reinforced with PP shown in figure 24. GC was disappeared

very quickly, and residue was less than MGC reinforced polymer. The mechanical grinded

21

glass fiber was left out with filler after recycling. So it was hard to maintain composition of

composite. It shows mechanical recycling was not feasible way of treating glass composites.

Figure 25: Comparison of MGC with (90%PP and 10%MAPP) and MGC with PP

Figure 25 represents comparison of MGC with (90% PP and 10% MAPP) and MGC with pp

and There was no significant different in the curves. Only reinforced fiber was the key factor.

There was no significant change in decomposition temperature. Weight change and residual

are different among different composites. Use the recycling fiber was a good choice to

reinforce polymer, it can enhance the heat resisting property of product.

3.2 DIFFERENTAIL SCANNING CALRIMERTY RESULTS

22

Figure 26: Comparison of DSC Graphs

Table 8: DSC curves of PP and Glass fiber compsites

Sample Melting Point

°C

Calorific Value

J/g

Crystallization Percent

%

PP 165.58 78.45 37.54

Virgin Glass Fiber 165.34 54.63 26.14

Hammer Milled +PP 165.54 52.35 25.05

GC+PP 165.28 57.95 27.73

MGC+MAPP 164.93 47.83 22.88

MGC(Coat) MAPP 164.63 64.91 31.06

NGMGC-MAPP 165.45 62.43 29.87

NGMGC(Coated)-MAPP 164.41 60.19 28.80

The melting point and glass transition temperature are comapredoin the graph shown in

figure 26 and the values are listed in table 8. The DSC curves of microwave pyrolysed glass

fiber reinforced with polypropylene , polypropylene and virgin glass fiber are compared in

the figure24 . The crystallization temperature was increased, when recycled glass fibers were

added to polyprolylene. It shows that adding recycled glass fiber have a nucleation effect on

PP. but addition of recycled glass fibers on PP reduce the crystallation percentage. The

23

polypropylene has a higher crystallization percent than the polypropylene reinforced with

recycled glass fiber. The non grinded and coated glass fibers have releatively higher values,

when compared with other batches. It shows longer fiber have higher nucleation effect thant

the shorter fibers reinforced with PP .The calorific values are also corresponds with

crystallization percentage. The 165°C melting temperature was not affect by addng of

recycled glass fibers.

3.3 DMTA RESULTS.

The dynamic mechanical thermal analysis was carried out on one sample in each batch .The

properties obtained from the dynamic mechanical thermal analysis are the storage modulus,

loss modulus and tan delta that was recorded from the temperature funtioned from - 60 to 140

.

Figure 27: DMTA curve for Microwave pyrolysed glass fiber with polypropylen

DMTA curve for MGC with PP shown in figure 27. The storage or elastic modulus w

ratio of the elastic stress to strain. The loss modulus was the ratio of the viscous stress

strain. Tan delta was the ratio of loss modulus to the storage modulus. This measure th

damping ability of the material. These data helps in measuring the glass transition

temperature. It was the temperature at which reversible change between rubbery and g

state of the polymer occurs. [23]

When storage modulus was more than loss modulus, the sample was undergoes

deformation. It always happened during -60°C to 0°C.When storage modulus curve a

Storage modulus

Loss modulus

Tan delta

e

as the

to the

e

lassy

elastic

nd loss

24

modulus curve coincide on a point, the material was semi-solid. It happened around

0°C.When the storage modulus was less than loss modulus, the sample was mainly viscous

deformation.28 It mostly happened from 0°C to140°C.

The highest values of storage modulus or stiffness values are obtained in the region - 60° C to

- 30° C. So the stiffenss values are measured from a general temperature of -50° C for all the

samples. The results are magnified in the scale from - 80° C to 80° C in x axis and 1500 MPa

to 4500 mpa in y axis to have better resolution.

Table 9: The DMA datas

Sample Stiffness at -50°C

GPa

Glass Transition Temperature

°C

PP 2.33 16.97

Virgin Glass Fiber 4.55 13.20

Hammer Milled Fiber 4.15 15.55

MGC-PP 4.23 13.96

GC-PP 3.6 15.23

NG-MGC-PP 4.48 14.72

NG-MGC-MAPP 4.28 14.92

Coating NG-MGC-MAPP 4.45 13.50

From the table 9 .It shows the refference sample virgin glass fiber has the highest stiffeness

values. The neat polypropylene has the lowest stiffness values. From the test it has shown

that adding glass fibers improves the mechanical properties of polypropylene. Non grinded

MGC with polypropylene and coated non grinded MGC with MAPP has the higher stiffness

values, when compared with other samples. The mechaincal recycled glass composite (GC)

has an average results when compared with microwave pyrolysed glass composite. When the

microwave pyrolysed glass fibers was grinded to a size it losses it’s mechanical properties

Based on DMTA testing coated NG-MGC reinforced polymer (90%PP and 10% MAPP) was

the best combination. The glass transition temperature for all the samples remains same.

25

3.4 FLEXURAL RESULTS

Flexural test was carried out for five samples in each batches and compared with the virgin

samples like Polypropylene and Virgin Glass Fibers. The flexural results were compared

according preparation methods of recycled glass fibers.

COMPARISON OF MICROWAVE GLASS FIBERS WITH POLYPROPYLENE AND

MALEIC ANHYDRIE POLYPROPYLENE

Figure 28: Comparison of Flexural Modulus of MGF reinforced with 10 % MAPP and PP

Figure 29: Comparison of Flexural Modulus of MGF reinforced with 10 % MAPP and PP

Table 10 . Comparison of Flexural Strenght of MGF Reinforced with MAPP and PP

Samples

Flexural Modulus Gpa

Standard Deviation

Flexural Strenght Mpa

Standard Deviation

Flexural propeties of glass fibers r

and 29 and details were tabulated in table 10.

reinforoced with Polypropyene and Maleic anhydride polypropylene. The microwave

pyrolysed glass fibers reinforced with MAPP has a higher flex

with microwave pyrolysed glass fibers reinforced with PP. In the methods of preparation

adding 10% of MAPP incresed flexural strenght of the composites. The flexural strenght of

composites was increased from 48.88 MPa,48.58 MPa a

57.82 MPa, when MAPP was

COMPARISION OF GRINDING METHODS OF MICRO

Figure 30: Comparison of Flexural Modulus of Grinding Methods of MGC

0

0.5

1

1.5

2

2.5

3

3.5

PP

Flex

ural

Mod

ulus

Gpa

26

Comparison of Flexural Strenght of MGF Reinforced with MAPP and PP

MGC NGMGC NGMGC CR

PP MAPP PP MAPP PP

Flexural Modulus Gpa 2.71 2.73 2.40 2.99 2.60

Standard Deviation 0.16 0.11 0.55 0.08 0.21

Flexural Strenght Mpa 48.88 55.91 48.58 57.25 44.83

Standard Deviation 1.71 2.74 4.29 0.65 0.65

Flexural propeties of glass fibers reinforced with MAPP and PP were compared in figure 28

and 29 and details were tabulated in table 10. Microwave Pyrolysed glass fibers are


pyrolysed glass fibers reinforced with MAPP has a higher flexural modulus when compared



composites was increased from 48.88 MPa,48.58 MPa and 44.83 to 55.91 MPa, 57.25 MPa,

reinforced with the compooistes.

ING METHODS OF MICROWAVE GLASS FIBERS

Comparison of Flexural Modulus of Grinding Methods of MGC

MAPP PP MAPP PP

MGC NGMGC Hammer Milled Fiber

Comparison of Flexural Strenght of MGF Reinforced with MAPP and PP

NGMGC CR

MAPP

2.80

0.12

44.83 57.82

2.69

were compared in figure 28

Microwave Pyrolysed glass fibers are


ural modulus when compared



nd 44.83 to 55.91 MPa, 57.25 MPa,

WAVE GLASS FIBERS

Comparison of Flexural Modulus of Grinding Methods of MGC

PP

Hammer Milled Fiber

Figure 31: Comparison of Flexura

Table 11 : Comparison of Flexural Properties Coated and Non Coated Glass Fiber

Samples


Standard Deviation


Standard Deviation

Flexural properties of Grinding methods of glass fibers

and data’s were tabulated in table 11.

grinding methods. The glass fibers are grinded in knife mill which reduc

to 3 mm. Non grinded fibers have fiber length of 10 to 25mm and

a fiber length of ±10 mm. The Non grinded fibers and

flexural properties when compoared with grinded composites.

composites was increased from 48.88 and 55.91 to 48.58, 57.25 and 55.84

0

10

20

30

40

50

60

70

PP

MGC

Flex

ural

Str

reng

ht M

Pa

27

Comparison of Flexural Strenght of Grinding Methods of MGC

Comparison of Flexural Properties Coated and Non Coated Glass Fiber

MGC NGMGC

PP MAPP PP MAPP

2.71 2.73 2.40 2.99

0.16 0.11 0.55 0.08

48.88 55.91 48.58 57.25

1.71 2.74 4.29 0.65

properties of Grinding methods of glass fibers were compared in figure 30 and 31

and data’s were tabulated in table 11.The flexural properties varied according to the types of

grinding methods. The glass fibers are grinded in knife mill which reduces the fibers to 0 .5

Non grinded fibers have fiber length of 10 to 25mm and hammer milled

The Non grinded fibers and hammer milled

ural properties when compoared with grinded composites. The flexural strenght of

composites was increased from 48.88 and 55.91 to 48.58, 57.25 and 55.84

MAPP PP MAPP PP

MGC NGMGC Hammer milled fiber

l Strenght of Grinding Methods of MGC

Comparison of Flexural Properties Coated and Non Coated Glass Fiber

Hammer milled Fiber

PP

3.02

0.13

55.84

2.34

were compared in figure 30 and 31

properties varied according to the types of

es the fibers to 0 .5

hammer milled fibers have

Fibers have higher

The flexural strenght of

GPa.

PP

Hammer milled fiber

The flexural Strenght of Grinded and non grinded glass fibers was almost same when it as

reinforced with Polypropylene, but danish hammer milled showed a higher flexural strenght

than both the fibers. But nongrinded glass fiber has higher flexural propeti

when it was reinforced with MAPP.

COMPARISON OF COATED AND NON COATED GLA

Figure 32 : Comparison of Flexural Modulus of Coated and Non Coated Glass fiber

Figure 33: Comparison of Flexural Modulus Coated and Non Coated Glass Fiber

0

10

20

30

40

50

60

70

PP MAPP

MGC

Flex

ural

str

engh

t Mpa

28



than both the fibers. But nongrinded glass fiber has higher flexural propeti


D AND NON COATED GLASS FIBERS

Comparison of Flexural Modulus of Coated and Non Coated Glass fiber

Comparison of Flexural Modulus Coated and Non Coated Glass Fiber

MAPP PP MAPP PP MAPP

MGC Coated NGMGC NGMGC



than both the fibers. But nongrinded glass fiber has higher flexural propeties than grinded

Comparison of Flexural Modulus of Coated and Non Coated Glass fiber

Comparison of Flexural Modulus Coated and Non Coated Glass Fiber

PP

NGMGC Coated

29

Table 12: Comparison of Flexural Properties Coated and Non Coated Glass Fiber

Samples MGC MGC Coated NGMGC

NGMGC Coated

PP MAPP PP MAPP PP MAPP PP MAPP


2.71 2.73 2.14 2.15 2.40 2.99 2.50 3.01

Standard Deviation 0.16 0.11 0.17 0.06 0.55 0.08 0.15 0.09


48.88 55.91 46.24 47.05 48.58 57.25 48.93

Standard Deviation 1.71 2.74 14.60 1.36 4.29 0.65 0.44

In figure 32 nad 43 tensile properties coated and non coated glass fibers were compared and

the data’s were tabulated in table 12. The recycled Glass fibers were coated with a sizing

material are compared with the non coated fibers. There was no significant difference in

flexural propeties between non coated and coated fibers. It was hard to coated grinded glass

fibers because of small and powdered fibers. The sizing material doesn’t evenly coated on

glass fibers because of these condition. Which made the fibers stick to each other. So the

fiber was grinded again in a small blender and made it as a poweder. So it has very less

flexural properties.

COMPARISON OF DIFFERENT COMPOSITION OF GLASS FIBERS

Figure 34: Comparison of Flexural properties of different compositions

Flexural Modulus Mpa

Flexural Strenght MPa

30

Table 13 : Comparison of Flexural Properties of different compositions of glass fibers

Samples NGMGC MAPP

NGMGC 20% MAPP

NGMGC 40%- 20% MAPP

NGMGC CR – 20% MAPP

NGMGC CR Coated 20%

MAPP

Flexural Modulus

GPa 2.99 2.60 3.40 1.99 2.48

Standard Deviation

0.08 0.16 0.22 0.24 0.05

Flexural Strenght

MPa 57.25 54.16 57.58 51.24 50.81

Standard Deviation

0.65 1.93 1.64 2.06 0.99

Comparison of Flexural properties of different compositions was shown in figure 34 and

details are listed in table 13. The different composition of glass fibers are used to improve the

mechanical properties . The flexural strenght was reduced from 57.25 MPa to 54.16 MPa,

when MAPP composition was Increased from 10% to 20%. When 40% glass fiber was

added with 20% MAPP, there was no significant difference. But it had higher flexrual

modulus than the Glass Fibers reinforced with 20% MAPP.

3.5 TENSILE RESULT ANALYSIS

Tensile test was carried out for five samples in

samples like Polypropylene and Virgin Glass Fibers. The tensile results were compared

according preparation methods of recycled glass fibers same as flexural results

COMPARISON OF MICROW

MALEIANHYDRIE POLYPROPYLENE

Figure 35. Comparison of E

Figure 36. Comparison of Tensile Strenght Glass Fibers Reinforced with 10% MAPP and PP

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

PP

MGC

E-M

odul

us G

Pa

31

RESULT ANALYSIS

Tensile test was carried out for five samples in each batches and compared with the virgin



COMPARISON OF MICROWAVE GLASS FIBERS WITH POLYPROPYLENE AND

OPYLENE

Comparison of E- Modulus Glass Fibers Reinforced with 10% MAPP and PP

Comparison of Tensile Strenght Glass Fibers Reinforced with 10% MAPP and PP

MAPP PP MAPP PP MAPP

MGC NGMGC NGMGC CR

each batches and compared with the virgin



PROPYLENE AND

Modulus Glass Fibers Reinforced with 10% MAPP and PP

Comparison of Tensile Strenght Glass Fibers Reinforced with 10% MAPP and PP

MAPP

NGMGC CR

Table 14 . Comparison of Tensile

Samples PP

E- Modulus GPA 2.64

Standard Deviation 0.218

Tensile Strenght Mpa 31.76

Standard Deviation 1.34

Tensile propeties of glass fibers r

and 36 and details were tabulated in table 14.

flexural properties.The microwave pyrolysed glass fibers reinforced with MAPP has a higher

tensile propeties when compared with microwave pyrolysed glass fibers reinforced with PP.

the tensile strenght of the composites was increased, when 10% of MAPP added. The t

strenght of composites was increased from 31.76 MPa,30.62MPa and 35.51 to 32.83 MPa,

39.10, 36.65 MPa, when MAPP

COMPARISION OF GRINDING METHODS OF MICRO

Figure 37. Comparision Of E

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

PP

E-M

odul

us G

Pa

32

Tensile propeties of glass fibers reinforced with MAPP and PP

MGC NGMGC NGMGC CR

MAPP PP MAPP PP

4 2.99 2.78 3.57 3.32

218 0.48 0.42 0.33 0.24

31.76 32.83 30.62 39.10 35.51

1.34 1.42 1.84 2.29 0.25

Tensile propeties of glass fibers reinforced with MAPP and PP were compared in figure 35

tabulated in table 14. These tensile results corresponds results with

The microwave pyrolysed glass fibers reinforced with MAPP has a higher


the tensile strenght of the composites was increased, when 10% of MAPP added. The t


39.10, 36.65 MPa, when MAPP was reinforced with the compoistes.

ING METHODS OF MICROWAVE GLASSFIBERS

Comparision Of E- Modulus of Grinding methods of Microwave glassfibers

MAPP PP MAPP PP

MGC NGMGC Hammer milled Fibers

einforced with MAPP and PP

NGMGC CR

MAPP

2.84

0.34

36.65

3.96

compared in figure 35

These tensile results corresponds results with

The microwave pyrolysed glass fibers reinforced with MAPP has a higher


the tensile strenght of the composites was increased, when 10% of MAPP added. The tensile


WAVE GLASSFIBERS

Modulus of Grinding methods of Microwave glassfibers

PP

Hammer milled Fibers

Figure 38. Comparision Of Tensile Strenght Grinding methods of glassfibers

Table 15: Comparision of Tensile properties of Grinding methods of glass fibers

Samples

E- Modulus GPa

Standard Deviation

Tensile Strenght Mpa

Standard Deviation

Tensile properties of Grinding methods of glass fibers

data’s were tabulated in table 15.

higher tensile properties properties when comp

strenght of composites was increased from 31.76 and 32.83 to 30.62 , 39.10 and 36.77.

The tensile Strenght of Grinded and non grinded glass fibers reinforced with polypropylene

was almost same, but danish

than both the fibers. But nongrinded glass fiber has higher tensile propeties than grinded


0

5

10

15

20

25

30

35

40

45

PP

MGC

Tens

ile S

tren

ght M

Pa

33

Comparision Of Tensile Strenght Grinding methods of glassfibers

ion of Tensile properties of Grinding methods of glass fibers

MGC NGMGC

PP MAPP PP MAPP

2.65 2.99 2.77 3.57

0.21 0.48 0.41 0.33

31.76 32.83 30.62 39.10

1.34 1.42 1.84 2.29

Tensile properties of Grinding methods of glass fibers were compared in figure 37 and 38 and

d in table 15. The Non grinded fibers and hammer milled

properties when compared with grinded glass fibers. The tensile



same, but danish hammer milled glass fibers showed a higher flexural strenght



MAPP PP MAPP PP

MGC NGMGC Hammer milled Fibers

Comparision Of Tensile Strenght Grinding methods of glassfibers

ion of Tensile properties of Grinding methods of glass fibers


PP

3.55

0.16

36.77

1.49

figure 37 and 38 and

hammer milled Fibers have

ared with grinded glass fibers. The tensile



glass fibers showed a higher flexural strenght


PP


COMPARISON OF COATED

Figure 39:Comparison of E

Figure 40 : Comparison of tensile

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

PP MAPP

MGC

E-M

odul

us G

Pa

34

AND NON COATED GLASS FIBERS.

Comparison of E-modulus of Non coated and Coated glass fibers

Comparison of tensile strength of Non coated and Coated glass fibers

MAPP PP MAPP PP MAPP PP

MGC Coated NGMGC NGMGC Coated

modulus of Non coated and Coated glass fibers

of Non coated and Coated glass fibers

MAPP

NGMGC Coated

35

Table 16: Comparission of Tensile properties of Non coated and Coated glass fibers

Samples MGC MGC Coated NGMGC

NGMGC

Coated

PP MAPP PP MAPP PP MAPP PP MAPP

E- Modulus GPa 2.65 2.99 2.47 3.02 2.78 3.68 3.19 3.57


Tensile Strenght

Mpa 31.76 32.83 35.71 33.71 30.62 39.10 34.45 36.01


In figure 39 nad 40 tensile properties coated and non coated glass fibers were compared and

the data’s were tabulated in table 16. The recycled Glass fibers were coated with a sizing

material are compared with the non coated fibers. The coated fiber has higher tensile

properties than non coated fibers when Reinforce with Polypropylene but it tensile properties

reduced or remains same when it was reinforced with MAPP. When Propylene was

reinforced, the tensile strenght increased from 31.76 MPa to 35.71 MPa and from 30.62 MPa

to 34.45 MPa. When MAPP was reinforced, the tensile Strenght reduced from 39.10 MPa to

36.01 MPa and remains same in grinded glass fibers.

COMPARISON OF DIFFERENT COMPOSITION OF GLASS FIBERS

Figure 41: Comparison of tensile Properties different composition of Glass fibers

E-Modulus Mpa

Tensile Strenght MPa

36

Table 17 : Comparison of tensile Properties of different compositions of glass fibers

Sample NGMGC MAPP

NGMGC Coated MAPP

NGMGC 20% MAPP

NGMGC 40%- 20% MAPP

NGMGC CR – 20% MAPP

NGMGC CR Coated

20% MAPP

E- Modulus GPa

3.68 3.57 4.18 5.23 2.99 4.18

Standard Deviation 0.33 0.29 0.34 0.40 0.24 0.41

Tensile Strenght MPa

39.10 36.01 34.7 39 36.99 36.53

Standard Deviation

2.29 2.81 2.20 1.98 4.37 2.57

Figure 41 shows the comparison of tensile propeties of different composition of glass fibers.

The data’s were tabulated in table 17. The composites were prepared from different

composition of glass fibers to improve the mechanical properties . The tensile strenght was

reduced from 39.10 MPa to 34.7 MPa, when MAPP composition was Increased from 10% to

20%.when the glass fiber composition was increased from 30% to 40% , there was no

significant difference. But it has a higher E- modulus than the Glass Fibers reinforced with

20% MAPP.

37

3.6 SUMMARIZATION OF RESULTS

Figure 42: Comparison of flexural, tensile and storage modulus(GPa)

Table 18 : Summarization of results

Sample

Storage modulus

GPa

Flexural modulus

GPa

E modulus

GPa

Flexural strenght

MPa

Tensile strenght

MPa

PP 2.33 1.61 2.21 46.59 40

CACO3 3.89 2.30 2.85 52.31 30.07

VIRGIN GLASS FIBER

4.55 4.68 6.13 90.07 56.2

NGMGC -MAPP

4.28 2.99 3.68 57.84 39.1

NGMGC COAT- MAPP

4.45 3.01 3.56 36.01

HAMMER MILLED-PP

4.15 3.02 3.55 55.84 36.77

NG 40%- MAPP 20%

4.77 3.40 5.23 57.58 39

E-modulus

Flexural modulus

Storage modulus

38

In figure 42, the recycled glass composite fibers were compared with reference sample. The

data’s were tabulated in the table 18. Adding glass fibers to polypropylene improves the

mechanical properties than the regular filler like CaCO3. Microwave pyrolysed glass fibers

have lower mechanical properties than virgin glass fibers. This shows that the glass fibers

losses it’s properties due to heating. The storage modulus (stiffness values) has almost

significant values. But flexural results and tensile results have much variance, which may due

to presence of char in the microwave pyrolysed glass fibers. The microwave pyrolysed glass

composite acquires brittle properties because of char. Increasing the glass fiber composition

40% improves the stiffness values but the flexural and tensile strength remains same.

3.7 FRACTIONAL DISTILLATION OF OIL

The polymer oil extracted during microwave pyrolysis has many compounds in small

concentrations. It affects the results in the GCMS showing many peaks in the graphs.

Therefore, in order to get clear results of the composition of the pyrolysis oil, and to separate

valuable components, this can be used for chemical industrial or other applications. It was

better to use fractioned distillation for polymer oil before GC-MS testing.

The polymer oil was heated inside flask, and a distillation column was connected to the flask.

The oil was stirred with a magnetic stirrer; the fractioned distillation oil was collected in a

vacuum while heating the oil in a bath gradually. The vacuum was 50mbar.

The experimental set up was presented in :

Figure 43: Distillation Experimental

39

Each fraction can be analyzed by GC-MS.

The first fraction of GC-MS spectrogram was shown in figure:

Figure 44: The first fraction of GC-MS spectrogram

It was very difficult to separate the chemical components. Because there are many different

compounds present in the fraction. As can be seen, many peaks occur in the first fraction of

spectrogram.

In the each fraction, the compounds tabulated in table 15:

Table 15: GC-MS data’s for Fraction distillation of the pyrolysis oil

Fraction Temperature of the oil batch Composition

1 22-60˚C

4-methyl benzaldehyde

Toluene

1-ethyl-2-nitro benzene

1-ethynyl-3-methyl benzene

Alpha-methylstyrene

2 60-70˚C

Benzene

Toluenepropylbenzene

Alpha-methylstyrene

40

3 70-83.5˚C

Benzene

Toluene


Alpha-methylstyrene

2-butenyl-benzene

Indene

4 83.5-101.9˚C

Benzene

Toluene

Bicyclo [4.2.0] octa-1,3,5

triene, 3-methyl


Benzoic acid

Benzene, 1,1’-(1,3-propanediyl) bis-

5 101.9-150˚C

1,2,5,7-cyclooctatetraene

Benzaldehyde

Alpha-methylstyrene

Benzocycloheptatriene

Dimethyl phthalate

1,1’-biphenyl, 3-methyl-

Benzene, 2,4-pentadiynyl

Aromatic compounds mainly exist in each fraction. So, the aromatic resins were used for

glass fiber composites, such as epoxy resins and unsaturated polyester. Because the polymer

oil consists of aromatic component, it seems like solvent, not useful oil. Compare with

commercial oil, it has too many different chemical composites. Thus, its application was still

limited.

41

Styrene was largely consisted in the pyrolysis oil. It was present at around 15 wt.-% . Such as

Alpha-methylstyrene , It was a very useful component after be distilled. Recovering styrene

can be used on an industrial basis. But it would probably not be economically feasible,

because very little styrene can be recovered from 1kg glass fiber composites. There has a

production relation among 1kg glass fiber, pyrolysis oil and styrene. Around 170g pyrolysis

oil from 1kg glass fiber, only 25g styrene can be recovered from 170g oil. Although it can be

recovered by distillation, it was not a good way since styrene was a cheap chemical.

4. CONCLUSION

Microwave pyrolysis was one of the feasible ways to recycle glass composite fibers .The

recycled glass fibers have lower properties when compared with the virgin glass fibers. It was

due to thermal stress the material undergone during microwave pyrolysis. The non grinded

and hammer milled fiber has a better mechanical properties than knife miller fibers. There

was not much significant difference in sizing the recycled glass fibers. But it helps in

materials to get stick to each other, which reduces pollution. Adding 10 % of maleic

anhydride polypropylene in PP improves the mechanical properties. it is possible that lower

ratios of MAPP can work better which will be evaluated in coming studies

A probably better way of utilizing the pyrolysis oil was convert the oil into synthesis gas. Its

abbreviation was syngas. Syngas was a mixture of hydrogen and carbon monoxide. 29

Hydrogen gas has a great potential as future fuel, it was a potential way to decrease CO2

emissions. Besides syngas as fuel, it was used as chemical feedstock to chemical industry,

and also can produce methanol and acetic acid. But syngas can be obtained by gasification of

renewable sources, such as natural gas, coal generally. So, converting polymer oil into syngas

can replace old method and use the resource in sustainable way.

42

5. REFERENCE

1. Goodman, S.H., Handbook of thermoset plastics. Second ed1998, New Jersey: Noyes

Publications.

2. Per Dannemand Andersen, Mads Borup, and T. Krogh, Managing Long-term

Environmental Aspects of Wind Turbines: a Prospective Case Study in the

International Journal of Technology, Policy and Management. 2007. 7(4).

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44

6. APPENDIX

TGA curve

Reference Sample curve

PP Virgin Glass Fiber

CaCO3 + PP Hammer Milled MGC(Denmark)

MGC (210˚C) MGC (800˚C)

45

GC (210˚C) GC (800˚C)

MGC (without char) (800˚C)

Testing Sample curve

GC + MAPP GC+PP

46

MGC+MAPP MGC+PP

Coated MGC + MAPP Coated MGC + PP

MGC-(without char) + MAPP MGC-(without char) + PP

47

Coated NG-MGC+MAPP Coated NG-MGC+PP

Coated NG-GC+MAPP Coated NG-GC+PP

NG-MGC + MAPP NG-MGC + PP

48

NG-MGC+20%MAPP NG-40%MGC+20%MAPP

MGC-(without char) +20%MAPP Coated MGC-(without char) +20%MAPP

DSC curve


Virgin Glass Fiber PP

49

Hammer Milled MGC(Denmark) CaCO3 + PP


MGC + PP GC + PP

NG-MGC + PP NG-MGC + MAPP

50

Coated NG-GC+MAPP Coated NG-GC+PP

Coated NG-MGC+PP Coated NG-MGC+MAPP

MGC + MAPP GC + MAPP

51

Coated MGC + PP Coated MGC + MAPP

NG-MGC+20%MAPP NG-40%MGC+20%MAPP

MGC-(without char) +20%MAPP Coating MGC-(without char) +20%MAPP

MGC-(without char) + PP MGC-(without char) + MAPP

52

DMA curve


PP Virgin Glass fiber

CaCO3 + PP Hammer Milled MGC(Denmark)


MGC + MAPP MGC + PP

53

GC + MAPP GC + PP

NG-MGC + MAPP NG-MGC + PP

Coated NG-MGC + PP Coated NG-MGC + MAPP

54

Coated NG-GC + MAPP Coated NG-GC + PP

Coated MGC + PP Coated MGC + MAPP

MGC(without char) + PP MGC (without char) + MAPP

55

NG-MGC + 20%MAPP 40% NG-MGC + 20%MAPP

MGC(without char) + 20% MAPP Coated MGC(without char) + 20% MAPP

DMTA Values

Sample Stiffness

MPa

Glass Transition Temperature

_

PP 2329 16.97

CaCO3 with PP 3886 15.03

Virgin Glass Fiber 4553 13.20

Danish Fiber 4154 15.55

GC-MAPP 3427 14.21

GC-PP 3603 15.23

MGC-MAPP 3899 14.72

MGC-PP 4230 13.96

MGC-(without char)-MAPP 3810 15.36

56

MGC-(without char)-PP 4012 14.95

Coating MGC -MAPP 3509 13.52

Coating MGC-PP 3632 12.28

NG-MGC-MAPP 4278 14.92

NG-MGC-PP 4482 14.72

Coating NG-MGC-MAPP 4451 13.50

Coating NG-MGC-PP 4025 15.55

Coating NG-GC-MAPP 3606 14.72

Coating NG-GC-PP 3711 13.21

NG-MGC-20%MAPP 4455 15.42

NG-40%MGC-20%MAPP 4766 15.01

MGC-(without char) 20%MAPP

4171 14.22

Coating MGC-(without char)-20%MAPP

4225 14.08

57

Flexural test

Sample Modulus (Gpa)

SD Flex

Strength MPa

SD Strain at Max %

SD

pp 1.61 0.15 46.59 2.58 6.29 0.28 CaCO3 2.30 0.07 52.31 2.75 4.76 0.51

Virgin glass fiber

4.68 0.29 90.07 6.02 3.20 0.16

Danish fiber 3.02 0.13 55.84 2.34 4.56 0.34 GC-MAPP 2.78 0.05 61.24 0.24 4.78 0.19

GC-PP 2.79 0.12 50.70 0.83 4.53 0.12 MGC-MAPP 2.73 0.10 55.91 2.74 4.53 0.21

MGC-PP 2.71 0.16 48.88 1.71 5.49 0.08 MGC-(without char)-MAPP

2.79 0.20 57.81 2.69 4.85 0.16

MGC-(without char)-PP

2.60 0.12 44.83 0.65 5.62 0.14

MGC COAT- MAPP

2.15 0.06 47.05 1.36 5.43 0.07

MGC COAT- PP

2.14 0.17 46.24 14.60 5.34 4.63

NG- MGC- MAPP

2.99 0.08 57.24 0.64 4.74 0.24

NG- MGC- PP 2.40 0.54 48.58 4.29 5.11 1.82 NG-MGC-

COAT MAPP 3.01 0.09 21.23 0.44 12.28 0.52

NG- MGC- COAT PP

2.50 0.15 43.93 11.93 5.53 3.78

NG- GC- COAT MAPP

2.60 0.08 58.27 0.69 4.99 0.13

NG- GC- COAT PP

2.58 0.14 51.87 1.50 4.70 0.04

NG-MGC-20% MAPP

2.60 0.16 54.16 1.93 5.13 0.16

NG-40%MGC-20%MAPP

3.40 0.22 57.58 1.64 4.12 0.38

MGC-(without char) 20%

MAPP 1.99 0.24 51.24 2.06 5.43 0.24

MGC-(without char)-COAT-20% MAPP

2.48 0.05 50.81 0.99 5.21 0.04

58

Tensile test

Sample

Tensile Strength Mpa

E-Mod Mpa

S.D Tensile Strength

S.D E - Mod

RESULTS TS

RESULTS E-MOD

Strain at max %

PP 40

2211

4.049086

138.7912

39.79 44.15 36.06

2362 2089 2182

7.182 8.55 8.65

8.12733 CaCO3

with PP 30.07

2847

1.674

204.66 28.18

31.39 32.42 30.68 30.77 28.88 28.15

2735 3045 3068 3031 2783 2531 2734

3.719 4.1264 4.43

5.513 4.83 5.03 4.02

4.524 Virgin Glass Fiber

56.2

6129.667

4.86621

718.6441

61.8 53.8 53

5923 5537 6929

2.44 1.66

0.449 1.516333

Danish Fiber

36.768

3546.6

1.49113

163.4879

37.91 37.5 34.9

35.43 38.1

3650 3763 3339 3490 3491

3.929 3.905 5.59 5.24 5.55

4.8428

GC-MAPP

38.385

3271

0.4946

569.1801 38.29

38.82 37.47 38.96

2777 2707 4095 3505

3.36 3.56 1.01 2.89

2.705

GC-PP 32.948

3025.8

0.597637

122.3426

33.03 33.48 32.17 32.52 33.54

3053 3109 2956 3158 2853

4.109 4.122 4.36 4.56 4.28

4.2862

59

MGC-MAPP

32.83

2994.8

1.424728

479.6235

34.96 31.47 33.53 31.81 32.38

2915 3696 2507 3224 2632

1.48 2.7

3.33 2.81 3.33

2.73 MGC-PP 31.765

2643.5

1.336924

218.3796

30.64 30.65 33.3

32.47

2724 2630 2351 2869

6.39 5.79 6.15 6.15

6.12 MGC-(without char)-MAPP

36.65

2844.667

3.957765

343.8958

32.4 37.32 40.23

3213 2532 2789

4.14 5.1

4.49

4.577

MGC-(without char)-PP

35.505

3323.5

0.246103

238.4932

35.38 35.87 35.34 35.43

2970 3489 3435 3400

7.08 6.25 6.03 6.19

6.388

Coated MGC -MAPP

33.71

2463

1.4641

81.44 31.64

32.43 32.92 34.96 35.8

34.24 33.95

2373 2462 2496 2528 2529 2527 2329

5.15 5.65 5.41 6.48 6.76 5.61 6.66 5.96

Coated MGC-PP

35.712

3025.8

2.756605

80.41642

39.36 37.95 33.23 34.26 33.76

2936 2807 2802 2804 2964

5.2 5.76 5.73 4.37 4.58

5.128

NG-MGC-MAPP

39.104

3679.8

2.288052

331.3845 35.88

37.55 40.53 40.29 41.27

3313 3771 3458 4177 3680

3.52

3.6

3.86

3.35

3.66

3.598

60

NG-MGC-PP

30.62

2776.4

1.839946

418.169 30.23

28.13 33.27 30.47

31

2253 3306 2539 2716 3068

6.28

2.17

5.89

5.79

5.93

5.212

CoatedNG-MGC-MAPP

36.014

3567.8

2.812531

298.951 33.48

34.09 40.63 35.62 36.25

3274 3401 3912 3869 3383

4.55

4.87

4.92

4.41

4.86

4.722

Coated NG-MGC-PP

34.45

3192.4

2.031428

131.6465

36.66 32.66 32.94 33.33 36.66

3388 3209 3021 3189 3155

7.04

5.47

6.45

6.09

6.52

6.314

Coated NG-GC-MAPP

41.576

3237.6

2.029465

224.7817

42.7 40.91 43.33 38.32 42.62

3539 3349 3227 3131 2942

3.57

3.67

3.75

3.76

3.96

3.742

Coated NG-GC-PP

34.74

3395

1.774934

195.2769

35.69 36.69 32.69 33.11 32.31 34.74

3466 3346 2987 3281 3041 3395

3.67

3.74

3.83

3.04

3.58

4.009

3.645

NG-MGC-20% MAPP

34.7

4182.2

4.099366

342.2159

35.73 27.57 38.03 36.53 35.64

4006 4484 3891 3913 4617

2.62

0.789

2.55

4.38

0.656

2.199

NG-40%MGC-20% MAPP

38.998

5234

2.772962

402.5506 39.7

41.69 34.66 35.96 38.1

4838 5601 5713 4895 5123

2.35

2.09

1.71

1.82

1.91

1.976

61

MGC-(without char) 20%MAPP

36.99

2997.4

2.011927

246.5163

35.24 35.1

40.03 37.55 37.03

2956 2780 3373 2787 3091

4.55

4.25

3.78

4.92

4.33

4.366

Coated MGC-(without char)-20% MAPP

36.534

4185.5

1.30412

412.0433

33.27 37.89 34.86 36.09

36

3948 4347 4373 3571 4451

1.4

1.97

2.71

4.38

2.41

2.574

Distillation

Polymer oil with other solvents

Polymer oil with Dichloromethane

Composition Quality

Toluene 91

1,3-Dioxolane, 2-ethyl-4-methyl- 83

Benzaldehyde 91

Alpha-Methylstyrene 97

Diphenylmethane 89

Dimethyl phthalate 97

Bibenzyl 91

62

Polymer oil with Chloroform

Composition Quality

1,3-Dioxolane,2-ethyl-4-methyl- 83

Benzaldehyde 91


Azulene 93


Benzene, 1,1-(1,3-propanediyl) bis- 97

Polymer oil with Hexane

Composition Quality





1H-Pyrazole-3-carboxaldehyde,5-phenyl- 86

63

Polymer oil with Methanol

Composition Quality




1,2-Diphenylcyclopropane 97

101119-1 with Dichloromethane

Composition Quality


Benzenebutanenitrile 83


1101052 with Dichloromethane

Composition Quality

Toluene 96




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RECYCLING OF GLASS FIBER COMPOSITES