AN INDUSTRIAL TRAINING REPORT

IN
M/s. LG POLYMERS INDIA PRIVATE LIMITED VISAKHAPATNAM

A STUDY ON GLOSS PROPERTY

SUBMITTED BY BHUPENDRA SINGH RAVI BHUSHAN

THIRD B.TECH PLASTIC TECHNOLOGY

DEPARTMENT OF PLASTIC TECHNOLOGY HARCOURT BUTLER TECHNOLOGICAL INSTITUTE , KANPUR

June-July-2006

ACKNOWLEDGEMENTS

It is with great happiness that I place on record my profound sense of gratitude to Mr. Mahesh Marwaha AGM, Technical Services and R&D for giving me an opportunity to carry out project in this company and for his guidance and spontaneous encouragement and suggestions throughout my training program. I express my thanks to Mr. Brian Taylor Manager, Technical Services and R&D, for their support and help during my stay in LG Polymers India Pvt. Ltd. I express my thanks to all TS personnel for their kind cooperation and healthy work environment provided to me through out my project work. I am also thankful to Mr. U.B. Ramayya, Deputy Manager, Quality control department for providing all the necessary facilities to carry out the experiments for my project work.

CONTENTS

I. II.

COMPANY PROFILE Basic chemistry of Styrene

1-2 3-4 5-8 6 7-8 8

9-12

III.
A. B. C.

General Purpose Polystyrene (GPPS)

Ingredients used in GPPS Description of the process Applications and Properties IV. High Impact Polystyrene (HIPS) A. Ingredients used in HIPS B. Description of the process C. Applications and Properties

10 11-12 12 13-16 14 15-16 17-20 21-35 36-62

V.
A. B.

Expandable Polystyrene (EPS)

Ingredients used in EPS Applications and Properties

vi. Processing methods vii. Testing methods

VIII. Results and Discussion

I. COMPANY PROFILE : L.G. Polymers (I) Pvt. Limited LGPI is one of the leading manufactures of Polystyrene (Trade Name LGSTRENE) and Expandable Polystyrene (Trade Name LGEXPOL). Company was established in 1961 as Hindustan Polymers for manufacturing of Styrene monomer, Polystyrene and its copolymers at Visakhapatnam. The Company was under DCM and then merged with MC Dowell & Co. Ltd. Of UB Group in 1978. Company was taken over by LG chem. (Korea) in July 1997. Henceforth it was renamed as LG Polymers (I) Pvt. Limited. Company was accredited with ISO 9001 2000 & ISO 14001 1996, certification from BVQI. LGPI is committed for ultimate customer satisfaction. LGPI is now an advanced company with implementation of SAP and carrying out activities like TPM, Six Sigma, QCs Suggestions and My Factory / My area and thus by introducing latest managerial tools marching ahead towards quality enhancement. Over the years the company has been subjected to many Major revamps and developments and increased its production capacities over the period. LGPI is committed to accomplish the goal of ultimate customer satisfaction by creating the values for the customer. LGPI is also actively involved in six sigma activities to achieve the best in quality. Over the years the company has gained a multi dimensional strength. Modernization is under taken as an on going process leading to quality and productivity. PRODUCTS - Manufacture: LGSTRENE 1. General Purpose Polystyrene {GPPS} 2. High Impact Polystyrene {HIPS} LGEXPOL 3. Expandable Polystyrene
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Total approximate capacity of the plant is:

PLANT GPPS HIPS EPS TOTAL

TOTAL CAPACITY / ANNUM (MT) 43,800 43,800 18,250 1,05,850

BASIC CHEMISTRY OF STYRENE INTRODUCTION: Polystyrene is one of the most widely used thermoplastic materials ranking behind polyolefins and PVC. Owing to their special property profile, styrene polymers are placed between commodity and speciality polymers. Since its commercial introduction in the 1930s until the present day, polystyrene has been subjected to numerous improvements. The main development directions were aimed at co polymerization of styrene with polar co monomers such as acrylonitrile, (meth) acrylates or maleic anhydride, at impact modification with different rubbers or styrene-butadiene block copolymers and at blending with other polymers such as polyphenylene ether (PPE) or polyolefins. Polystyrene (general-purpose polystyrene GPPS) can be understood as a linear polyethylene chain with laterally attached phenyl rings, being responsible for the enhanced glass transition temperature and high refractive index. Stiffness, brilliance, gloss and hardness are the main characteristics of the material. Consequently applications such as audio/video cassette packs, beakers, transparent food packaging, shower cabinets, lamp covers, etc., are dominant. To overcome the brittleness of GPPS, the material was modified by incorporation of polybutadiene. Impact-modified polystyrene (IPS) was invented by Ostromislensky and has been commercialized since the 1950s. IPS consists of polystyrene matrix with embedded cellular rubber particles. By rubber toughening. However, transparency is lost. The use of styrene-butadiene block copolymers instead of plybutadine results in translucent impact polystyrene with core/shell particle morphology. These particles are small and thus reduce scattering of visible light. Enhanced property demands in the packaging sector and also in the electric and automotive sectors require improved product properties. Homogeneously miscible blends with, e.g. Polyphenylene ether (PPE) combine the excellent processability of the amorphous polystyrene with the thermal stability of its blend partners.

Styrenic copolymers are materials capable of thermoplastic processing which, in addition to styrene (S), also contain at least one other monomer in the main polymer chain. Styrene-acrylonitrile (SAN) copolymers are the most important representative and basic building blocks of the entire class of products. By adding rubbers to SAN either ABS (acrylonitrile butadiene-styrene) or ASA (Acrylate-styrene-acrylonitrile) polymers are obtained depending on the type of rubber component employed. These two classes of products yield blends composed of ASA and polycarbonate (ASA + PC) or ABS and polyamide (ABS+PA). MABS polymers (methacrylate-acrylonitrile-butadiene-styrene) together with blends composed of polyphenylene ether and impact-resistant polystyrene (PPE/PS-I) also form part of the styrenic copolymer product range. A characteristic property is their amorphous nature, i.e. high dimensional stability and largely constant mechanical properties to just below the glass transition temperature, Tg. POLYMERIZATION: Styrene is one of the easiest monomers to polymerize and of course this led to the early discovery and commercialization. It is one of the few monomers able to be polymerized under free radical, anionic, cationic and metal catalyzed conditions. This is due to low polarity of the styrene molecule and to the resonance stabilization of the growing polystryryl species in the transition state.

CH2 - CH3 + CH2 = CH2 Benzene Ethylene

AlCl 3 900C

Ethyl Benzene
600 - 650 0C Fe O - H2 (Dehydrogenation) Mg O (catalyst)

CH = CH2
Purified by distillation

Styrene

GENERAL PURPOSE POLYSTYRENE (GPPS) III. GENERAL PURPOSE POLYSTYRENE (GPPS) General Purpose polystyrene also called polystyrene. It has high clarity and dimensional stability is useful in day-to-day life. General-purpose polystyrene is polymerizing by Bulk polymerization. In this process styrene is partially polymerized batch wise process. In which heating the monomer in large vessels at about 800c until 50% conversion is attained. The viscous solution of polymer in monomer is then fed continuously into the top of the tower, which is some 25 feet high. The top of the tower is maintained at a temperature of about 100 degree centigrade the center at about 1500c and the bottom at about 1800c as the feed material traverses the temperature gradient, polymerization occurs and fully polymerized material emerge from the base of the tower. The reaction is controlled by a complex array of heating and cooling jackets and coils with which the tower is fitted. The molten material is fed into an extruder, extrudate as filament and cooled and chopped into granules. Since the products contain few impurities, it has high clarity and good electrical insulation properties. A. Ingredients added in General purpose polystyrene:1. 2. 3. 4. 5. 6. 7. 8. Plasticizer Chain transfer agent Lubricant Toners Tincher Optical brightner Initiator MFI Controller

Short name Density Properties Applications

GPPS : 1.04 g\cc : High clarity, Dimensional stability : CD cover, Audio Cassettes, Refrigerator Crispers, jewel boxes, Food packaging etc.

B. Description of GPPS process: The main process involved in GPPS Manufacturing is as given below: -

Feed preparation Polymerization Extrusion

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Pelletisation Product packing

Feed preparation: - Known quantities of styrene & additives are add to feed preparation tank and then agitated for a minimum period of one hour FPT styrene is transferred to Feed Solution Tank (FST) through filter to avoid external contamination entry and to filter any undissolved particles Polymerization: - polymerization is done in two steps 1. Pre-Polymerization in Kettles 2. Polymerization in Towers 1. Pre-Polymerization : Feed is supplied to kettles from FST through ring mains. The total capacity of the kettle is 19m3. Mass temp is enormously maintained up to 120-140 c by method of evaporative cooling. Condensate lines from kettle condensers are provided with collecting pots to separate accumulated water. This water is drained frequently. 2. Polymerization : Pre-polymerized material is subjected to tower type reactor for further polymerization. Tower reactor is divided in to five zones numbered serially from top to bottom. First zone is provided with cooling water jacket. Balanced zones are provided with stabbed in steam coils. Vapors from tower are condensed in tower head condenser and the Condensate liquid is collected in pure monomer tank (PMT). De volatilizer pre-heater: Polymer from tower is pumped to DVPH. In DVPH, the temp. is raised to 200230C so as to flash off volatiles & residual monomer. Vacuum is maintained at a very high level. De- volatilizer: After separating volatiles, in DV excess monomer is strip off. DV is operated under vacuum of minimum 710mm Hg. Extrusion & Pelletisation: DV bottom polymer is pumped through die- head to under water strands granulate (USG). In USG system product strands are cut into 3x3 mm size pellets under circulating water & dried in drying section & screened for oversize &under size if any. External lubricant is added using vibrato feeders. Product Packing: From silo, product is packed in bags of 25 kg net weight by automatic/ manual electronic weighing machine, stitched & stacked on pellets & stored. C. Applications of GPPS :
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CDs boxes Audio cassettes Crispers trays Refrigerator applications Jewelry boxes House hold articles Food packaging etc.

HIGH IMPACT POLYSTYRENE (HIPS) IV. HIGH IMPACT POLYSTYRENE (HIPS) For many polymer applications polystyrene is considered to be too brittle. Because of this PS manufacturers have made a number of attempts to improve the polymer in this aspect. The most successful approach to this problem has been the addition of rubbery materials to the polymer and rubber modified polystyrene commonly known as impact polystyrene. Several rubbers have been tried for the preparation of impact polystyrene and rubber has a pro found effect on the properties of the product simple blending of the two polymers for ex. In an internal mixer or two roll mill gives a product which has commonly slightly better impact strength than polystyrene likewise the mixing of polymers in latex form the isolation of the product by coagulation results only in marginal improvement. However much better results are obtained if polystyrene is prepared in the presence of rubber. In one commercial process, for ex. , Rubber is dissolved in a styrene - solvent mixture and then styrene is polymerized in solution. By this process the resultant blend will not only rubber attached to the rubber molecules this gives a marked improvement in the impact strength that can be obtained it has been demonstrated that the SBR polystyrene blends the rubber should exists in discrete droplets where a good finish is required, with in the polystyrene matrix. In such a form the rubber can reduce crack propagation. For a suitable blend following features are necessary. a) b) The rubber and polystyrene should not be too compatible. If they are there will be molecular mixing and no improvement in toughness. The rubber should not be too incompatible if good rubber polystyrene Adhesion is to be obtained.

A. Ingredients added in high impact polystyrene: 1. 2. 3. 4. 5. 6. 7. Impact modifier Diluent Plasticizer Anti Oxidants Lubricant Chain transfer agent Initiators
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8. Optical brightener 9. UV Stabilizer 10. Chain transfer agent Short name Density Properties Applications : HIPS : 1.04 g/cc : Toughness, Good processability, Re cyclibility. : PC bodies, Printer bodies, Toys, Novelties, Disposable cups etc.,

B. Description of HIPS process : The main process involved in HIPS manufacturing is as given below: Styrene Solvent rubber Lubricant Chemicals Toners Feed solution (Input) Polymer Feed preparation Polymerization Extrusion Packing

FEED PREPARATION

feed solution (output) Polymer (Output) strands

POLYMERIZATION

EXTRUSION

Strands

PELLETISATION

Pellets

Pellets

PRODUCT PACKING

Lot

Feed preparation section: - Feed preparation section consists of rubber grinder, rubber pneumatic conveying system, and rubber dissolvers with agitators, solution storage tanks & recycle monomer tanks.

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Rubber grinder: - a predetermined quantity of styrene monomer is metered into the rubber dissolved. These are cut into 1/2" or 3/4" pieces & fed to rubber dissolver. Rubber dissolver: - additives are added to the rubber dissolver. All contents are agitated for 6-8 hrs. Storage tanks: - The styrene + rubber is known as dope solution which is pumped to solution storage tanks. Polymerization section: - this section consists of six continuously stirred tank reactors (CSTRs), DVPH & DV. Extrusion & packing section: - The molten PS from DV bottom is pumped through the screen changer which is a slide plate type having a provision for fixing two screens in which the contamination particles are removed. The polymer from the screen enters the under water palletizing system through die head. From die head PS strands are guided into pelletizer chamber & cooled by water. Strands are palletized into cylindrical pellets. Then to the driers. In the driers blowing air blows off the moisture from those pellets. The pellets fall into a rotary valve of the product conveying system where they are send to silos. External lubricant is added in the pellets at the valve outlet. The pellets are packed into bags with laminated inside with an automatic bagging machine. C. Application of HIPS : Refrigerator table tops Washing machine front panel protector Vacuum cleaner housings Sanitary & House ware Air conditioner Toys, COLOURATION OF GPPS AND HIPS It consist of floataire mixer , feed hopper , extruder with barrel heaters , cooling trough, palletiser , vibrating screen ,lube mixer , collecting bin . In floataire mixer required quantity of natural polystyrene pallets, colour pigments are mixed for sufficient period to have homogeneous mixture. From there it is fed to hopper. From hopper material is fed to extruder in a controlled way. The mixture in molten state , comes out in the form of strands from die head. These strands are cooled, cut into pallets in palletiser, screened for undersize and oversize product in vibrating screen. The coloured product is mixed with external lubricant in lube mixer and collected in a drum. This product is packed in bags of 25Kg net weight. Ball pen barrel, Umbrella handles, Wall clock frames, Air cooler front panel TV Cabinets Audio cabinet & Video Cassettes

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EXPANDABLE POLYSTYRENE (EPS) V. EXPANDABLE POLYSTYRENE (EPS) Expandable polystyrene has become very important as a thermal insulating material and to a lesser extent as a packaging material. It may be prepared in various ways but most commercial methods make use of Expandable polybeads. In one process, styrene is polymerized by suspension process, using a low boiling hydrocarbon such as n-pentane, is added to the system this modification results in the formation of polystyrene beads containing 5-8% of the volatile hydrocarbon . Alternatively, slurry of performed polystyrene beads may be treated under heat and pressure with the volatile hydrocarbon. The impregnated beads are expanded, commonly by treatment with steam. When the beads are heated in steam, they soften and valorization of the low boiling hydrocarbon and diffusion of steam into the beads cause the beads to expand to about forty times than their original size. The expanded beads are called as prepuff. The prepuff then allowed to stand so that air permeates into them and they attain atmospheric pressure at room temperature. The prepuff are subsequently loaded into a mould through which steam is passed, they again expand and being enclosed in the mould, are consolidated into a block. A. Ingredients used in EPS Production: 1. 2. 3. 4. 5. 6. 7. 8. 9. Suspending Media Monomer Suspending Agent Suspending Aids Low temperature and high temperature initiators Nucleating agent Blowing Agent Chain transfer agent Optical brightner

EPS Coating chemicals and their significance: Anti lumping agent: This is used to prevent the lumps in pre puff while pre expanding and not to cause choking by the lumps problem. In batch process of pre expander it will from cake and it may not use full for moulding.

Fusion chemical: This chemical is used to give good fusion of prepuff during moulding. Fusion chemical is generally a powder of low melting point, while moulding due to steam the low melting point present on the bead will melt and thus the surface of two beads will fuse at same time and the residual pentane in pre puff bounder against each other that will help in fusion and after cooling the well fused article will obtain.
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Anti static agent: In the name itself it act as anti static chemical. The polarity of the anti static coating (due to higher concentration of hydrophilic group) attracts moisture thus providing an effective path to dissipate static charge during transportation and screening of polystyrene beads. Self-extinguishing coating chemical: These chemicals are generally brominates compound, which on burning will from an bromine blanket around the burning Eps article and it will cut of the oxygen around the fire and extinguish fire by absent of oxygen. Oil coating : This is used for coating to provide water repellent property to the EPS. B. Properties & Application : Properties :-

Low thermal conductivity Low moisture absorption rate and air permeability Low sp. gravity Superior construction (e.g., processing and adhesion) Excellent fire and corrosion resistance Mechanical strength of reasonable level Not generating toxic gases. No quality degradation during life cycle Uniform quality Cost effective construction Lightweight / convenient handling

Applications: Boxes for agricultural / fishery products Seedling trays Floats Disposable cups Insulation purpose Novelty items Ceiling purpose PROCESSING & TESTING METHODS
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Processing Methods: 1. INJECTION MOULDING :For testing the mechanical properties of thermo plastic materials, some testing methods are adopted to check their specification limits. Usually, product of polystyrene is obtained in the form of resin. So, by using resin we cannot test the properties. Some specimens with required dimensions are needed to test those properties. As a part of this, Injection moulding is best suitable method to mould specimens for testing. In injection moulding, a definite quantity of molten thermoplastic material is injected under pressure into a relatively cold mould where it solidifies to the shape of the mould. The process consists of feeding the compounded plastic material as granules, pellets or powder through the hopper at definite time intervals into the hot horizontal cylinder where it gets softened. Pressure is applied through a hydraulically driven piston to push the molten material through a cylinder into a mould fitted at the end of the cylinder. While moving through the hot zone of the cylinder, a device called torpedo helps spread the plastic material uniformly around the inside wall of the hot cylinder and thus ensures uniform heat distribution. The molten plastic material from the cylinder is then injected through a nozzle into a mould cavity. One is stationery and other is moving part. The stationery part is fixed to end of the cylinder while the movable part is can be opened or locked on to the stationery part. A proper flow of the molten material to the interior regions of the mould is achieved by preheating the mould to an appropriate temperature. Usually, this temperature is slightly lower than the softening temperature of the plastic material undergoing moulding. After the mould is filled with the molten material under pressure, then it is cooled by cool water circulation and then opened so as to eject the moulded article.

2. COMPRESSION MOULDING : The press consists of a pair of platens, which have arrangements to be heated up individually. The top platen is attached to a stationary head. The platens carry the mould halves. The moving head moves up or down by sliding on the pillars on either side of the press. A ram actuated by a hydraulic system moves the moving head. At the bottom below the stationary head operates another ram. This bears the ejector pin mechanism of the bottom half of the mould. A control panel ahs all the required switches arranged on it. The switch on button and switch stop button the press. The platen temperature indicators and control switches to operate the and bottom hydraulic rams. The independent hydraulic system actuating lines. The downstroking press has one disadvantage. In case of failure of the hydraulic system. There is the danger of the
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operators hand getting trapped or smashed in between the mould halves or platens. Hence, some times up stroking presses are used in which hydraulic failure causes the bottom ram and the platen to full down keeping the press open. Also, there are presses with side-ram. Of the two platens, one being moving type and other a stationary one. Compression presses may be operated manually or in a fully automatic manner. In the automatic systems, the various operations are sequentially synchronized to carry out the job. A typical cycle of operation for stroking presses may be follows. 1. A master batches moulding compound, in the form of powder or granules, is keeps ready platens are heated up. 2. Exact quantity of the feed (charge) is metered out by volume (volumetrically) or weight. 3. The charge is placed in the cavity. 4. Top hydraulic ram is operated to close the mould. 5. Immediately after closing the mould halves, it is opened for a fraction of a second and then closed. This is called degassing or breathing. 6. The mould is held closed for a predetermined period to complete. 7. The moulded article is cooled (for thermoplastics). 8. Actuating the proper hydraulic system ejects the article. 3. EXTRUSION : Extrusion is one of the cheapest methods available for producing many common plastic products such as films, filaments, tubes, sheets , pipes, rods, and straps, all in continuos length . the molten plastic under suitable condition is forced through the die orifice, which imparts the desired profile to the extrudate. Extrusion is a continuos process of converting the suitable raw material into a product of specific cross-section by forcing the material through an orifice or die under controlled conditions. In this machine, the compounded plastic material is fed through the hopper as either powder or granules into a cylinder having provision for electrical heating for softening the material. The hot plastic charge is further worked through the cylinder by a Helically revolving screw. The material passed from hopper to die through different zones named feed zone, compression zone, and metering zone. No heating takes place in feed zone . In compression zone, however , the powdered charge melts due to the heat conducted from the heating elements and is compressed by working of the screw. The melted material is then sent to the metering section, where it requires a constant flow rate, imparted by helical screw. The pressure build up in this section enables the polymer melt to enter the die and emerge out of it with the desired profile. The extrudate material of required profile emerging from the die is quite hot and has to be cooled rapidly to avoid deshaping. The extrudate is accordingly carried over a conveyor belt through a tub containing cold water. The product formed is cut to desired length wound on to rolls . The extrudate process is also used for coating wires and cables with P.V.C , or rubber and for coating roll-foamed metal strips with suitable thermoplastic.
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VII. Testing Methods: i) MELT FLOW INDEX (MFI) Test Method: The ASTM procedure is ASTMD-1238G. Definition: It is the rate of extruction of molten material through an orifice of specific length and diameter under prescribed conditions of temperature and weight. Significance: This method covers the measurement of the rate of extruction of molten resin through an orifice of specified conditions of temperature and pressure This method is particularly useful for quality control tests on thermoplastic having relatively low melt viscosity. The flow rate obtained with extrusion plastometer is not a fundamental property. It is an empirically defined parameter critically influenced by the physical properties and molecular structure of the polymer and the condition of measurement. The rhelogical characteristics of polymer melts depend on a no of variables. Since the values of these variables occurring in this test may differ substantially from those in large-scale process, test results may not correlate directly with processing behavior. Apparatus: The apparatus used is an extrusion plastometer type made by Tinious Olsen Company. The apparatus shall be a dead wt position plastometer construction a thermostatically controlled heated cylinder with an orifice at the lower end and a weighted piston operating within the cylinder (note-1). The temperature set up in the cylinder is about 200 degrees. The orifice diameter is 2.1mm. Test Procedure: Check the calibration status of melt Indexer. Take approximately 5 0.5 g. of sample. Fill the barrel with sample with the help of rod. Place the position in the barrel in the top of the sample. Maintain 200 0.2c barrel temperature. Place 5-kg weight on the auto loader platform & press start. Record the MFI values after completion of the analysis. gm/10 min. at 200c. 5 kg load applied
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Units:

ii) TENSILE STRENGTH Test Method: ASTM D-638 Definition: It is the tensile load per unit area of minimum original cross section with in the gauge boundaries carried by the test specimens at any given moment. It is expressed in force per unit area in Kgf/cm2. Significance: This method is designed to produce tensile property data for the control and specification of plastic materials. These data may also be useful for material specification and qualitative characterization purpose and for research and development of plastics. Tensile properties may vary with specimen preparation and speed, of testing. Consequently, where precise comparative results one desired. Apparatus (UTM-Machine) The specimens are tested on universal testing machine made by Shimadzu a Japan company. In this UTM we can do three types of tests namely tensile testing, compression testing and flexural testing. Testing machine of constant rate of cross head-movement type and compressing essentially fixed member, Grips, Grips are for holding the test specimen between fixed member and movable member Specimen dimension: The specimen used to test the tensile properties is like a dumbbell shaped specimen as shown in below. The thickness of the specimen 3.16mm. The width of the specimen is 13.02mm. The length of the total specimen is 6 inches. The distance between the grips is maintained as 115mm. The crosshead speed is 50mm/min for HIPS. The crosshead speed is 6.3mm/min for GPPS. For each sample 3 specimens are tested for constancy and taken average of 3 specimens. The tensile strength and % of elongation was calculated and the stressed crack resistance of HIPS also calculated. Test Procedure: Using UTM machine can test tensile strength of a plastic material. The UTM consists of the two upper & lower Jaws. The upper jaw is movable while the bottom jaw is fixed.
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Measure the width and thickness of rigid flat specimens with a suitable micrometer to the nearest 0.025mm (0.01 in.) at a several points along their narrow section. Place the specimens in the grips of the testing machine taking care to align the long axis of the specimen and the grips with an imaginary line joining grips to the machine & Start the machine. Take a divider & point it on the bar. Increase divider length along with the bar movement. At a certain point, the material breaks. Take the readings & with the help of a divider take the % elongation. Units: Kgf /cm
iii) FLEXURAL STRENGTH

Test method: ASTM procedure is ASTM D-790 Definition: A bar of rectangular cross section is tested in flexural as a simple beam, the bar resting on two supports and the load applied by means of a loading nose midway between supports. Flexural strength is nothing but the ability of a material to withstand against the bending. The specimen is deflected until rupture occurs or until the max. Fiber strain of 5 percent is reached, which ever occurs first. Significance: Flexural properties determined by this method are especially useful for quality control and specification process. Reproducibility between specimens is approximately +/- 5% for materials tested under comparable conditions. However flexural properties may vary with specimen thickness, temp atmospheric conditions and differences in rate of straining. Apparatus (UTM machine): The specimens were tested on universal testing machine made by Shimadzu Company using win soft software. Loading nose and support shall have cylindrical surface, ignored to avoid excessive indention or compressive failure, that is max recoverable deformation or compressive failure due to the stress concentration directly under the loading nose. The radius of the nose and support shall be at least 3,2mm for all specimens. Specimen dimensions: The specimen is injection moulded rectangular bar width about 12.6mm and thick ness 3.16mm. The crosshead speed for HIPS is 1.3mm/min. span length is 50mm. For consistency 3 specimens for each sample to be tested and average is taken. Testing will be done after giving in 24 hours conditioning time from moulding. Test Procedure: A bar of rectangular cross section is tested in a Flexural as simple beam, the bar resting on two supports and the load applied by means of a loading nose midway between supports. Flexural strength is nothing but the ability of material to withstand against
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bending. The specimen is deflected until rupture occurs or until the maximum fiber strain of 5% is reached, which ever occurs first. Flexural strength Flexural strength can be calculated by following formula S=3PL/2bd2 Where S= Stress in outer fiber at mid point in Kg/cm2 P= Load at a given point in the load deflection curve Kg. L= Span length mm B= width of beam tested cm. D= depth of beam.

Units: Kgf / cm2 iv) IZOD IMPACT TEST Test method: ASTM procedure is ASTM D-256 Definition : a) The excess energy pendulum impact test indicates the energy to break standard test specimens of specified size under stipulated conditions of specimen mounting, notching, and rate of loading. b) The energy to break a standard test piece is act sum of several energies. 1) The energy to deform the specimen. 2) The energy to initiate fracture of the specimen. 3) The energy to propagate the fracture the specimen. 4) The energy to throw the free end of broken specimen. 5) The energy lost through friction and through vibration of apparatus and its base Significance: Scope of these methods of test are intended to determine the relative susceptibility to fracture by shock of plastic material and electrical installing materials as indicated by the energy expanded by a standard pendulum type impact machine in breaking one blow a standard specimen. Apparatus: The machine is of pendulum type. The pendulum shall be released from which a position that linear velocity of the center of striking edge at the instant shall be approx.11 feet per sec. Which corresponds to an initial elevation of this point of 2 feet.
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Means shall be provided for determining the impact value of the specimen, which is the energy expanded by the machine in breaking the specimen. The value is equal to the differences between energy in the pendulum blow and energy remaining in the pendulum after breaking the specimen, after correction has been made for wind age and friction. The specimens are injection moulded of thickness 1/4 th and 1/8th inch and the notch is made at the center by 1mm depth. The apparatus used is Izod impact made by Tinious Olsen Company. And the units are Kg/cm notches. The results are tabulated. Test Procedure: Using an Izod impact-testing machine can test impact strength of a material. At least five samples are to be taken for testing the impact strength. Notching must be done to the samples of which we are testing. Notching shall be done on a milling machine. Measure the width and thickness of each specimen with a vernier or a micrometer caliper and record its average width along with its identifying marking. Position the specimen precisely and rigidly but not too tightly clamped in the vise. Release the pendulum & note & record the excess energy remaining the pendulum after the breakage of specimen, together with a description of the appearance of the broken specimen.

Unit: Kg-cm/cm notch v) GLOSS Test method: ASTM D-2457 Speculer Gloss: The relative luminous fractional of a specimen at the secular direction. Luminous fractional reflectance: The ratio of the luminous flux reflected from to that incident on specified solid angles. Significance: Secular gloss is used primarily as a measure of the shiny appearance of floors and surfaces. Comparison of gloss values is meaningful only when they refer to the same measurement procedure and same general type of material. Gloss is complex attribute of a surface, which can t be completed measured by any single number. Speculer gloss usually varies with surfaces smoothness and flatness. It is sometimes used for comparative measurements of properties.
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Apparatus: Gloss meter consists of an incandescent light source finishing an incident beam means for locating the surface of the specimen and a receptor located to receive the required pyramid of rays reflected by the specimen. The receptor shall be a photosensitive device responding visible radiation. The axis of the incident beam shall be at one of the specified angles from the perpendicular to the specimen surface. The axis of the receptor shall be at the mirror reflection of the axis of incident beam. The instrument should be calibrated in every operation. The gloss is measured at any angle of 600.

vi) VICAT SOFTENING POINT (VSP) Test method : ASTM procedure is ASTM D-1525 Definition: The temperature at which a flat-ended needle of 1mm2 circular cross section will penetrate a thermoplastic under a specified load using a uniform rate of temperature rise. Significance: Data obtained by this method is used to compare the heat softening quantities of thermoplastic materials. Apparatus: The apparatus used in an automatic display of temperature type made by CEAST Company. The equipment consists of both types of measurements like Vicat softening point and heat distortion temperature. The equipment shall be consists of the following. Immersion bath: Bath for heat transfer liquid with stirrer, thermometers and heaters. The heaters should have controllers to permit manual or automatic of selected bath temperature risk rate. Heat transfer liquid: The liquid shall be of low viscosity and should have no short time effect at elevated temperature on the materials being tested. The oils like, silicon oil, Glycerine, ethylene glycol and mineral oil have used successfully for various plastics. 3 specimens support, weight and indicators, temperature indicator. Test specimens: The test specimen shall have a min. Width of 12.7mm and min.thickness of 3.2MM.

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Rate of the temperature rise is of 1200c/hr. Test Procedure: Place the specimen, which is at room temp on specimen support. So that it is approximately centered under the needle and gently lower the needle rod, so that the needle on the surface of the specimen, and hold it in position. The blacks of thermometer or thermocouple should be as close as practical to the specimen. Carefully lowered the assembly into the bath taking care not to it any way that would damage the specimen. Apply load, set the penetration indicator at zero. And starts temperature rise Record the temperature when indicator reads 1-mm penetration. CEAST Company made the apparatus, used to determine the VSP for all the samples by this apparatus and the results are tabulated. The specimens are injection moulding. Units: C

vii) FALLING DART IMPACT STRENGTH (F.D.) Test method : ASTM procedure is ASTM D 5420-96 Definition: This test method covers the determination of the relative ranking of materials due to energy required to crack or break flat, rigid plastic specimens by impact falling weight. Mean failure energy: The energy required producing 50%failure, equal to the product of the constant mass and mean failure height. Mean failure height: The height at which a standard mass, when dropped on test specimens, will cause 50%failure. Significance: Plastics are visco elastic and therefore may be sensitive to changes in velocity of weights falling on their surface. This test is usually depends on the geometry of falling wt, sticker and support. These results are greatly influenced on the quality of the specimen. The test specimen; the diameter or width of the flat specimens shall be at
22

least 25mm greater than the dia of the hole in support plate.(3.2mm). The thickness of the specimen in a whole sample shall not be more than 5 Test Procedure: Determine the number of specimens for each sample to be tested. Mark the specimens and conditions. Prepare the test apparatus for the geometry selected. Measure and record the thickness of each specimen in the area of impact. Choose the specimen of random from the sample, position the sample. The same surface areas are both the test specimens should be the targets each time. Place the test specimen on the tester anvil, after raising the weight and striker foot is sure the specimen is flat against the specimen. Support plate before the striker foot is brought in contact with the top surface of the specimen. Raise the weight in the tube to the desired impact value and release it so that the weight drops on the striker. Remove the specimen and examine it to determine whether or not it has failed. If the first specimen fails, decrease the drop height while keeping the mass constant. If the specimen does not fail here also increase the drop height one increment then test the second specimen. In this manner, select the impact height for each test from the results observed with specimen just tested. Test each specimen only once.

Units: Kg-m

23

A STUDY ON GLOSS PROPERTY

Definition:- Gloss is the relative luminous fractional reflectance of a specimen in the specular direction. luminous fractional reflectance:- The ratio of the luminous flux reflected from, to the incident on a specimen for specified solid angles Gloss theory:- Gloss of a surface is the ratio of light reflected from the surface to the light incident on the surface when the angle of incident and the angle of reflectance are equal but of opposite sign. Angles are measured from the plane vertical to the test surface. This type of reflection is called reflection or in contrast to diffuse reflection. In other words gloss is a measure of how well a surface functions as mirror. The perfect mirror do not exist. Some metals e.g. silver can be polished until they reflects secularly over 80% of light. Non-metallic surfaces such as paints are relatively poor mirror reflecting at best 5% to 10% specularly as usually viewed. Specular reflection is proportion to the angle of view. Difference in specular reflection are magnified at larger angles , allowing difference at low level to be measured. Conversely measurements at small angles are more suitable for detecting difference in reflection at high level. Specular reflection is influenced by smoothness(texture) of text source. Patches of the source scatter the reflected light, some of which may miss the receptor completely. Micro distortion such as waviness may distort images that otherwise approach perfection. Micro distortion such as scratches may give rise to diffuse reflection. Principle:- Glosso meter works on the principle of reflectance of a specimen at specular direction Equipment details :1. Manufacturer:- photoelectric instrument Pvt. Ltd. 2. introduction:- The equipment comprises of the following a) The main unit with a portable head b) Accessories:i) Set of high and low standards. ii) A secondary standard porcelain file. iii) Base plate for clothor thin paper sample. relative luminous fractional

24

3. General description & working of equipment:- The instrument consists of a light portable head connected by a leak transmitting into a -pin connector to sensitive digital panel meter. Light from a source (a filament lamp) is formed into a parallel beam by a lens and falls at a specified angle onto the sample. Specularly reflected light will be reflected at the same angle as incident beam. This light is made to fall on the lens, which forms an image of the source or the aperture. The image is of the same shape as that of source. To avoid the light which is not specularly reflected, an aperture is used. The light exiting the aperture is collected on the detector. The detector is mounted behind the aperture, the output from which is fed to the detector system. Sensitivity and zero are controlled and fitted on the front panel. The detector used is a potted silicon photocell. This has a reasonably long life and rarly if ever needed to be replaced. The unit is placed on the calibrated high gloss standard and sensitivity control is adjusted to get the marked reading of the standard. The corresponding reading when the head is placed on the test sample gives the specular gloss value of the test sample. The measuring unit is housed in a cabinet with accessories. A built in solid state power supply is provided which is fitted inside the cabinet. 4. Caliberation:- The unit is placed on the calibrated high gloss standard and sensitivity control is adjusted to get the marked reading (90) of the standard. Now the equipment is kept on the calibrated low gloss standard and sensitivity is controlled to get the marked reading (zero) of the standard. The corresponding reading when the head is placed on the test sample gives the specular gloss value of the test sample. 5. Procedure:i) ii) Placed the head centrally on the calibrated standard marked with high gloss value. Bring the reading to the value marked on the standard with the sensitivity control and place the head on the standard marked with the lower gloss value. If the reading coincide with the standard value within two units, the optical alignment of the head is correct. The gloss value of the test sample can now be ascertained by placing the head on the sample and noting the value directly. For normal routine work this value is fairly accurate, for day today working a glazed ceramic tile can be calibrated against the high and low standards, and used as secondary standard. At the time of standardization the porcelain plate or taking reading, care should be taken that the glazed surface is absolutely clean.

iii) iv)

6. Essential conditions for measuring gloss of flat surfaces:-

25

i) ii) iii)

The surface should be plane and smooth. It should be free from waviness and other flows. There should be no scratch on the surface.

7. Optical alignment:- To obtain consistent and accurate results from the instrument, it is absolutely essential that the optical alignment of the instrument is correct. Though the instrument is sent out from the factory properly aligned, there is possibility of the optical alignment getting altered in transit. Otherwise also it is suggested to check the optical alignment occasionally and must be carried out after a change of lamp. Optical alignment is carried out as followed i) Place the piece of the white paper underneath the base of the head. Slightly unscrew the two screw in the lamp housing tube and move the lamp mounting slightly up and down till the light spot is at centre in the base aperture and is also nearly covering it ii) Remove the photocell mount from the aperture tube and place a small piece of tissue paper on the top of the aperture opening. iii) Place the measuring head on a mirror or a glass plate and slightly unscrew the two screws meant for keeping aperture in position. iv) Move the aperture up and down till a sharp focused image of the filament on the tissue paper is formed. Now tighten the screw. Confirm that only exact aperture disc with the pin hole it by loosening the tightening screw on top of the disc and adjusting till the image passes out unobstructed. v) Fit the photocell mount on the top of the aperture. vi) Place the head on the calibrated gloss standards of high marked gloss value and adjust the reading of the value assigned to the standard. vii) Place the head on the lower value gloss standard and note the reading , if it is within two gloss units , the optical alignment is correct. Recheck to confirm. viii) In case the lower gloss value standard indicate much difference, move the aperture a trace higher or lower till the correct value is obtained. 8. Significance of different heads viz 20, 45, 60 heads:Different heads viz 20, 45, 60 means different angle of incident of light at 20, 45, 60 respectively, accordingly the angle of reflectance changes being equal in magnitude but opposite in direction. Increasing the angle of incidence increase the intensity of light recepted by receptor increasing the apparent gloss of the surface. 60 Head:Geometry- Light is incident at 60 and reflected at 60 . This is the most frequently used head. This head is most useful for the application where the gloss of surface is low and a grazing angle of incident increase the apparent gloss of the surface.

26

MOULDINGS OF SPECIMENS:A family mould consisting of a tensile bar, impact specimens of both and 1/8 inch , VSP bar, two flexural bars and one colour eye bar, was done on injection moulding machine made by CINCINNATI. For every samples about 50 moulds are taken out and the moulds were conditioned for 24hrs. , then the moulds are used for testing of properties.

Stages during which gloss gets affected:Effectively there are two stages during which the gloss property of any polymer changes, these stages are 1. Polymerisation stage 2. Processing stage

1. Polymerisation stage:- polymerisation is the process during which, monomer

combined to each other and form a high molecular weight compound called polymer. Polymers having different physical properties like tensile strength, flexural strength, brittleness, toughness, impact strength, gloss etc. Gloss is one of the most important properties of any polymeric material. in case of the HIPS gloss is more important property than most of the other polymers. Gloss property can be changed by the many factors during polymerisation. Important factors, which have good control over gloss property of any polymer, are i. Types of rubber used. ii. Level of rubber used. iii. Rubber particle size and particle size distribution iv. Gel content v. Swell index i) Types of rubber used:- when external forces works on HIPS, the rubber particle have a stress-relaxation action. To do this job, they must be bound sufficiently to the matrix and have sufficient elasticity.this means that rubber used must be capable of grafting and cross-linking. polybutadiene can used most frequently to fulfill this condition. Apart from pure polybutadiene rubbers, styrene-butadiene copolymers are also used, enabling products having particle size of less than 1 m to be produced. They have high gloss and high rigidity, but somewhat lower toughness for a comparable polybutadiene content. Many other rubber systems have also been commercially successful. Styrene block copolymers yield a HIPS product with a small particle size and provide high gloss. A mixed rubber system consisting of styrene butadiene block rubber and/or ethylenepropylene diene modified (EPDM) rubber can be blended with the polybutadiene to form bimodal rubber particle size distribution for a combination of high gloss and high impact. The block rubber generates the typical capsular small particles, and the EPDM, which is
27

incompatible with the block rubber, yields large particle as a separate rubber phase. EPDM with high degree of unsaturation and use for a high concentration of cross linking promoting peroxide (di-tert-butyl-peroxide) to stabilize the rubber particle is require improving grafting. Another example of an alternative rubber system is the asymmetric radial polymer (ARPS). ARPS has four equal arms of polybutadiene with a polystyrene segment attached to the one of the polybutadiene arms HIPS product made with ARPS blends polybutadiene produces two separate rubber phase with different morphologies and particle size distribution. The ARPS produces a capsular morphology and the polybutadiene produces a normal cellular morphology surrounded by a lamellar structure thats provides a reactor product with both high gloss and high impact. ii) Level of rubber used: - the rubber level used in the polymer controls gloss of the any polymer. Higher the rubber level, lower will be the gloss and lower the rubber level, higher will be the gloss. So to the higher gloss, we should use lower level of the rubber. But as we decrease the level of the rubber, impact strength will become lower. So there must be some optimum level of rubber, which would give both good gloss and high impact strength.
Effect of rubber level in HIPS

Rubber level(%) 7.1 8.8

Gloss at 60 95 60

Izod impact (ft-lb/in) 1.2 3.0

iii) Rubber particle size and particle size distribution:As the rubber particle size decreases, gloss increases and with the increase in the rubber particle size gloss decrease. The rubber particle size (RPS) range is essentially determined by three factors, namely the shear field of the reacting material during and immediately after the phase inversion, the viscosity ratio between the disperse and coherent phase and degree of grafting, which affect the interfacial tension. A decrease in viscosity of coherent phase result in increase in RPS and reduction in the stability of the oil-in-oil emulsion. An increase in grafting initially gives smaller cell particles and ultimate new particle structure. With increasing shear, the particle size decrease i.e. the particle size distribution peak shifts to lower value and relative proportion of smaller particle increases which result in better gloss. iv) Gel content:- Gel content is the fraction of the polymer, which is not soluble in solvent like toluene. The gel content of the polystyrene in the rubber, indicating the phase volume of crosslinking of the rubber. As the rubber particle size increases , crosslinking increases, which causes gel content to increase, resulting in lowering of gloss of the surface of the molded article.
28

v) Swell index:- swell index is the volumetric ratio of a swollen gel to its unswollen state . Swell index indicates the strength of crosslinking domain. As swell index increases, rubber particle size decreases, which cause the gloss to increase.
2.

Processing stage:- Processing is the stage during which the polymer gets
converted into desire final shape. Gloss property of the polymer is affected during the processing of the polymer. Their are some factors which affect the gloss property significantly during processing. these factors are

i) Barrel temperature:- In barrel there are four different zones a. Feed zone b. Compression zone c. Metering zone d. Nozzle By the variation of the temperature of these zones , we get different values of gloss. As we increase the temperature of different zones of barrel, gloss of the surface will increase. Reason: With increase in the temperature of different zones in barrel, gloss of the surface increases, probably due to decrease in viscosity of the polymer melt.

BARREL TEMPERATURE:TEMPERATURE ZONE NOZZLE ZONE1 ZONE2 ZONE3 T1 205 200 185 180 T2 210 205 190 185 T3 215 210 195 190 T4 220 215 200 195 T5 225 220 205 200

LGH-301 BARREL TEMP GLOSS SAMPLE1 SAMPLE2 SAMPLE3 AVERAGE T1 96.00 96.80 90.80 94.53 T2 99.00 100.80 101.10 100.30
29

T3 98.00 101.80 103.40 101.06

T4 104.60 104.80 105.10 104.83

T5 107.20 107.70 103.20 106.03

LGH-302 BARREL TEMP GLOSS SAMPLE1 SAMPLE2 SAMPLE3 AVERAGE T1 38.7 39.6 37.3 38.86 T2 46.7 38.0 40.3 41.66 T3 49.1 45.8 44.8 46.56 T4 50.7 51.7 54.8 52.4 T5 61.1 55.4 57.1 57.3

10 1.06

10 4.83

120 100 80 60 40 20 0

94 .5 3

10 6.03

10 0.3

46.56

52.4

57.3

38.86

41.66

LGH-301 LGH-302

T1

T2

T3

T4

T5

30

ii) Cooling time:- cooling time of the mold affects the gloss of the surface. As we increase the cooling time, gloss increase. Reason:

COOLING TIME(Sec.) LGH 301

TI=40

T2=45

T3=50

T4=55

T5=60

COOLING TIME T1 GLOSS SAMPLE1 99.20 SAMPLE2 106.30 SAMPLE3 104.30 AVERAGE 103.26

T2 99.70 100.80 99.80 100.10

T3 103.20 107.60 102.40 104.40

T4 107.80 104.60 106.50 105.66

T5 108.40 107.20 104.80 106.80

LGH-302 COOLING TIME T1 GLOSS SAMPLE1 61.30 SAMPLE2 58.70 SAMPLE3 53.00 AVERAGE 57.66 T2 46.80 28.70 57.40 44.30 T3 63.20 55.00 58.60 58.93 T4 60.60 64.50 64.20 63.10 T5 59.80 68.80 62.60 63.73

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10 5.66

10 3.26

120 100 80 60 40 20 0

10 0.1

57.66

58.93

63.1

63.73

10 6.8

104 .4

44.3

LGH-301 LGH-302

T1

T2

T3

T4

T5

iii) Injection velocity:- linear velocity of injection affects the gloss property of sample. As we increase injection velocity, gloss increases. Reason: this is due to increase in shear rate of the polymer. INJECTION V1=30 VELOCITY(mm/s) V2=35
32

the

V3=40

V4=45

V5=50

LGH-301 INJECTION VELOCITY GLOSS SAMPLE1 SAMPLE2 SAMPLE3 AVERAGE LGH-302 INJECTION VELOCITY GLOSS SAMPLE1 SAMPLE2 SAMPLE3 AVERAGE V1 50.70 54.50 53.40 52.86 56.30 50.20 57.40 54.63 52.40 56.10 57.70 55.43 56.00 53.90 57.80 55.90 64.40 63.57 60.30 62.75 V2 V3 V4 V5 V1 110.80 108.80 109.20 109.60 V2 111.60 111.80 111.30 111.73 V3 112.00 109.70 109.80 110.50 V4 113.10 112.60 113.00 112.76 V5 114.80 114.10 114.10 114.33

33

112.76

111.73

140 120 100 80 60 40 20 0

109.6

110.5

54.63

52.86

55.43

62.75

114.33

55.9

LGH-301 LGH-302

V1

V2

V3

V4

V5

iv) Hold time:- Time during which molded article is kept in mold before cooling starts is known as hold time. Reason:

HOLD TIME(Sec.) LGH 301

TI=2

T2=3

T3=5

T4=7

T5=9

HOLD TIME T1 GLOSS SAMPLE1 92.10 SAMPLE2 93.30 SAMPLE3 94.00 AVERAGE 93.13

T2 96.60 98.80 100.20 98.53

T3 102.10 102.50 102.10 102.23

T4 102.20 103.80 104.40 103.46

T5 104.50 102.70 101.40 102.86

LGH-302
34

HOLD TIME T1 GLOSS SAMPLE1 46.20 SAMPLE2 47.80 SAMPLE3 45.60 AVERAGE 46.53

T2 45.80 45.10 46.60 45.83

T3 46.20 45.50 47.60 46.43

T4 45.10 45.60 44.80 45.16

T5 40.20 41.80 41.20 41.06

102.23

103.46 45.16

120 100 80 60 40 20 0

46.53

93.13

46.43

45.83

41.06

102.86

98.53

LGH-301 LGH-302

T1

T2

T3

T4

T5

V) Number of shots:- with increase in the number of shots, gloss of the surface of
35

molded article increases. Reason: With increase in no. of shots mold temperature increases, which causes the viscosity of the polymer to decrease and the shear rate to go up.

LGH-301 NO. OF SHOTS S1 GLOSS 98.10 LGH-302 NO. OF SHOTS S1 GLOSS 37.30 S5 40.30 S9 45.10 S13 51.20 S17 51.20 S5 101.00 S9 104.00 S13 107.10 S17 108.20

100 80 60 40 20 0

98.1

101

104

120

107.1

108.2

51.2

37.3

40.3

45.1

51.2

LGH-301 LGH-302

S1

S5

S9

S13

S17

36

vi) Clamping force and mold finish:Clamping force and mold finish are the two important factors which significantly affect the gloss of the surface of molded article. If the mold is well finished then gloss will increase with increase in clamping force and if the mold is not well finished then on increasing clamping force gloss of the surface of the molded article will decrease.

There are some more factors which also affect the gloss of the surface of the molded article. 1. 2. 3. 4. Air Entrapment Melt index of the material Contamination Resin excessively moist

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