Petrochemical Corporation

JG SUMMIT

Polyethylene Laboratory Overview

Seadrift, Texas 1997

Scope
Service organization that provides process control testing of granular and pelleted resin, and product qualification testing.

A JG Summit Company
ISO 9001: 2000

Basic Introduction to Polyethylene

Polymerization
Ethylene + Catalyst = Polymer Chain
H C= H H C H H H H H H H H H H H H C C C C C C C C C C C CH3 H CH3 H CH3 H CH3H CH3 H CH3

Ethylene Molecule

This unit is repeated n times.

A JG Summit Company
ISO 9001: 2000

Basic Introduction to Polyethylene

Melt Index (MI)
Measurement of Molecular Weight
Molecular Weight Relative to Chain Length

Polymer Chains of Different Lengths

Longer Chains Make Extrusion More Difficult

Measured In Melt Index Plastometer

Forced Through Small Orifice Temperature & Weight Critical Less Material (by weight) Yields Lower Melt Index

A JG Summit Company
ISO 9001: 2000

Basic Introduction to Polyethylene

Molecular Weight Distribution (MWD)
Frequency of Chains With Different Lengths
Different Chain Lengths Yield Different Molecular Weights Narrow MWD Has Small Range of Chain Lengths Broad MWD Has Wide Range of Chain Lengths

Variations of Chain Lengths Create Distribution

This Variation Measured By Melt Flow Ration (MFR)

A JG Summit Company
ISO 9001: 2000

Basic Introduction to Polyethylene

Melt Flow Property Terminology
Melt Index uses 2.16 kg weight (44 psi) (I2)
5 kg weight (100 psi) for low melt index products (I5)

Melt Flow Index uses 21.6 kg of weight (440 psi) (I21)

Melt Flow Index/Melt Index Indicator of Molecular Weight Distribution (MWD)

A JG Summit Company
ISO 9001: 2000

Basic Introduction to Polyethylene

Molecular Weight & Molecular Weight Distribution

Narrow MWD

Medium MWD

Broad MWD

Molecular Weight

There are 3 basic types of curves that depict the distribution of molecular weight present in different resins.
A JG Summit Company
ISO 9001: 2000

Basic Introduction to Polyethylene

Molecular Weight & Molecular Weight Distribution
As MWD Broadens These Properties Increase, These Properties Decrease, Moldability Tear Strength Warpage Impact Strength Shrinkage Gloss Haze
The molecular weight distribution of a given resin has a pronounced affect on the fabricating behavior of the resin. The development or selection of a product for a particular application, involves a compromise of all these parameters to achieve the best balance of properties for that application.
A JG Summit Company
ISO 9001: 2000

Basic Introduction to Polyethylene

MWD & Product Applications
Narrow Molecular Weight Distribution
Application (LLDPE, HDPE) Film Extrusion Blow Molding Injection Molding Rotomolding

Medium Molecular Weight Distribution

Application (HPDE, LDPE, LLDPE, MDPE) Film Extrusion Blow Molding Pipe, Hose, & Tubing

A JG Summit Company
ISO 9001: 2000

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Basic Introduction to Polyethylene

MWD & Product Applications
Broad Molecular Weight Distribution
Application (HDPE, HMW-HDPE, MDPE) Film Blow Molding Pipe, Hose, & Tubing

Molecular Weight Distribution Classification

Class Very Narrow Narrow Medium Broad Very Broad MFR 20-32 32-50 50-80 80-130 >130
A JG Summit Company
ISO 9001: 2000

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Basic Introduction to Polyethylene

Crystallinity & Density
Density is a measure of the crystallinity of polyethylene. The higher the density, the higher the level of crystallinity. Density is a guide primarily to the level of mechanical properties.
0.910 0.925 0.926 0.940 0.941 0.960 Considered Low Density Considered Medium Density Considered High Density

A JG Summit Company
ISO 9001: 2000

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Basic Introduction to Polyethylene

Crystallinity & Density
Crystallinity is a measure of the ability of the molecules in the resin mass to orient themselves in ordered arrangements. When resin is fluxed or melted, the molecules lie in a somewhat tangled state with very little orderliness.

Amorphous State
A JG Summit Company
ISO 9001: 2000

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Basic Introduction to Polyethylene

Crystallinity & Density
As the resin cools, the molecules align themselves into ordered arrangements. The stronger the attraction between the molecules, the greater the degree of crystallinity. Density is the resin property used to indicate the degree of crystallinity in polyethylene.
amorphous crystalline

crystalline
A JG Summit Company
ISO 9001: 2000

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Basic Introduction to Polyethylene

Crystallinity & Density
Rigidity Melting Point Shrinkage Warpage Hardness Abrasion Resistance Tensile Yield Strength Haze Chemical Resistance Increasing Density
Properties that increase as density goes up
A JG Summit Company
ISO 9001: 2000

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Basic Introduction to Polyethylene

Crystallinity & Density
Tear Strength
Impact Strength

ESCR
Permeability

Elongation
Cycle Time Increasing Density
Properties that decrease as density goes up
A JG Summit Company
ISO 9001: 2000

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Additives
Stabilization Objectives
Control Changes In Melt Properties Discoloration Resistance Corrosion Protection Gel Prevention In-Service Performance Cost Effective Stabilization

Process Degradation Can Take Place During:

Melt Extrusion Storage Service Life
A JG Summit Company
ISO 9001: 2000

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Additives
Polymer Degradation Can Consist Of:
Chain Scission and Cross-link Reactions Incompletely Deactivated Catalyst Residuals Environmental Conditions Such As Temperature, Oxygen, and High Shear

Poor Stabilization Can Result In:

Poor MD Tear Strength Poor Color Poor Impact Strength Hazy Melt Increased Die Swell
A JG Summit Company
ISO 9001: 2000

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Additives
Classes of Stabilizers & Their Affects On PE
Anti-oxidants
Can improve melt property retention

Neutralizers
Work against corrosion Reduce gel formation Can improve color

Slip Agents
Used for coefficient of friction (how well two layers of film slide against surface of each other)

A JG Summit Company
ISO 9001: 2000

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Additives
Classes of Stabilizers & Their Affects On PE
Anti-block agents
Prevents layers of film from sticking to each other. The load required to separate two layers of film.

Processing Aids
Used to reduce melt fracture. Used to lower shear stress during extrusion. Can improve taste in some cases.

A JG Summit Company
ISO 9001: 2000

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Commercial Applications
Film Extrusion Materials
HDPE Film (UCAT-B, UCAT-G Catalyst)
Grocery Bags Sack Liners Shopping Bags

LLDPE Blown Film (UCAT-A, UCAT-J Catalyst)

Food Bags Grocery Sacks Food Packaging

A JG Summit Company
ISO 9001: 2000

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Commercial Applications
High Strength Film Resins
LLDPE Blown Film (UCAT-A, UCAT-J Catalyst)
Trash Bags Grocery Sacks Stretch Wrap Can Liners

LLDPE Slot Cast Film (UCAT-A Catalyst)

Diaper Film Bread Bags Stretch Wrap

A JG Summit Company
ISO 9001: 2000

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Commercial Applications
Blow Molding Resins
HMW-HDPE (UCAT-B, UCAT-G Catalyst)
Drums Shipping Containers Large Parts

UNIVAL Polyethylene Resins (UCAT-B Catalyst)

Chemical Bottles Dairy, Juice, & Water Bottles Oil Bottles

A JG Summit Company
ISO 9001: 2000

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Commercial Applications
Injection Molding Resins
HDPE (UCAT-A, UCAT-J Catalyst)
Housewares Crates Food Containers Drink Cups

A JG Summit Company
ISO 9001: 2000

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Commercial Applications
Pipe, Hose, & Tubing
LLDPE (UCAT-B Catalyst)
Drip Irrigation Flexible Pipe, Hose Flex Hose

MDPE (UCAT-B, UCAT-G Catalyst)

Small Diameter Water Pipe Municipal Gas Pipe

HDPE (UCAT-B, UCAT-G Catalyst)

Large Diameter Gas, Water, & Industrial Pipe Small Diameter Water Pipe

A JG Summit Company
ISO 9001: 2000

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Laboratory Testing
Melt Flow Properties Density Ash Bulk Density Contamination Pellet Uniformity Extractables (Hexane/Cyclohexane) Color (Hunterlab) Additive Content by UV/Infrared & X-ray Flourescence Spectroscopy
A JG Summit Company
ISO 9001: 2000

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Laboratory Testing
Film Appearance Rating (FAR) Tape Rating APS (Average Particle Size) Odor Environmental Stress Crack Resistance (ESCR) Bottle Weight Residual Volatile Hydrocarbon Mechanical Testing
Tensile Yield Tensile Strength Ultimate Elongation
A JG Summit Company
ISO 9001: 2000

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Laboratory Testing
Principle Structural Properties of Polyethylene For Reactor Control
Property Molecular Weight Crystallinity Control Test Melt Index (MI) & Melt Flow Index (MFI) Density

UNIPOL PE Technology Manual

Analytical & Contract Product Information Volume V, Book 2

ISO 9001: 2000

Methods Identified With PEG Nos. Equipment Identified with E Nos. Includes Optional As Well As Required Equipment Usually Referenced By known Vendor & Equipment Model Nos.
A JG Summit Company

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Physical Test Descriptions

Melt Index/MFI = PEG 302, 304, 305
Measure of the rate of extrusion of a thermoplastic through an orifice of specified length and diameter under specified conditions of temperature and pressure. This is an indicator of Molecular Weight.

Melt Flow Ration = PEG 304, 305

This is a calculated value. It is the Melt Flow Index divided by the Melt Index. This is an indicator of the Molecular Weight Distribution.

Density = PEG-300
Measured by the weight per unit volume of the polymer (g/cc or kg/m3). Measure of the degree of crystallinity in the polymer
A JG Summit Company
ISO 9001: 2000

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Physical Test Descriptions

Ash = PEG-306
Determines the inorganic ash content of polyethylene by burning off the polymer portion. Used as an indicator of catalyst productivity.

Bulk Density = PEG-301

The measure of weight per unit volume (lb./cubic ft or kg/m3). This property can change with particle size and type of catalyst Bed fluidization and conveying is affected by this variable

Contamination = PEG-504
Measure of contaminants caused by oxidized resin, external contamination, dirt, metal etc.. Determined by size and number of the contaminants.
A JG Summit Company
ISO 9001: 2000

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Physical Test Descriptions

Pellet Uniformity = PEG-505
A visual inspection to check that the pellets are reasonably uniform in size to minimize problems in extrusion at the customers location.

Hexane Extractable = PEG-801

Measure of low molecular weight polyethylene (oligomers), in resin used for food applications. Required for compliance with the FDA. Extractable limits apply to base resins without any additives.

Color = PEG-502
A measure of what is physically acceptable to the customer. Can be dependent upon the level of catalyst residue in granular resin.
A JG Summit Company
ISO 9001: 2000

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Physical Test Descriptions

Additive Content = PEG-400-411
Measure the amount of resin modifiers being added to the resin. Additives are added to prevent oxidation, act as UV stabilizers, or can be used as processing aids, or property enhancers.

FAR = PEG-510, 511

Film Appearance Rating subjective visual inspection for gels and imperfections. It is done to predict its fabrication and its aesthetic value. Gels can either be polymeric (high molecular weight polymers), or silica (residual catalyst).

Tape Rating = PEG-508

Visual inspection for gels (imperfections), 0.031 (0.79mm) or larger
A JG Summit Company
ISO 9001: 2000

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Physical Test Descriptions

APS = PEG-507
Measure of the particle size of the resin. Bed fluidization is affected by this variable

Odor = PEG-503
Test to evaluate the odor of polyethylene in pellet form. Odor can be defined as burnt, waxy, or acetic.

Environmental Stress Crack Resistance = PEG316

Test to determine endurance of plastic under the expected environmental extremes. For ESCR testing, the specimen is immersed in a strong detergent solution (Igepal) to accelerate the stress cracking phenomena.
A JG Summit Company
ISO 9001: 2000

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Physical Test Descriptions

Bottle Weight = PEG-315
Test to obtain swell characteristics of a test resin against a standard resin.

Residual Volatile Hydrocarbon = PEG-308

Test to determine the amount of residual hydrocarbons in polyethylene resin.

Mechanical Properties = PEG-317

Tensile yield Tensile strength Ultimate elongation
Associated with the reaction that results when a force or load (stress) is applied to a material
A JG Summit Company
ISO 9001: 2000

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Test Time Requirements

Test
Melt Index Melt Flow Ratio Density Ash Color Bulk Density Particle Size Contamination

Analytical Time
15 minutes 15 Minutes 60 Minutes 45 Minutes 20 Minutes 15 Minutes 15 Minutes 5 Minutes

Technician Time
5 Minutes 5 Minutes 5 Minutes 5 Minutes 2 Minutes 8 Minutes 5 Minutes

A JG Summit Company
ISO 9001: 2000

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Test Time Requirements

Test

Analytical Time

Technician Time
5-10 Minutes 15 Minutes 10 Minutes 30 Minutes 5 Minutes 30 Minutes 20 Minutes 25 Minutes

Antioxidant 25-60 Minutes Film Rating 40 Minutes N-Hex. Extr. 3 Hours Cycl. Extr. 4.5 Hours Tape Gel Rating 20 Minutes Bottle Weight 100 Minutes ESCR Days Tensile Prop. Days

A JG Summit Company
ISO 9001: 2000

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Quality Control
Calibration & Control Charting
Calibration are performed on all equipment. Reference standards are used for calibration verification. Control charts are used to track equipment performance.

Half-Blind Sampling
Used as tool for checking the ability of technicians to reproduce their analytical skills. Technician is informed of what kind of sample, but not given previous results.

Round-Robin Sampling
Sampling technique used for determining how well two or more laboratories are able to reproduce analytical testing. Can also compare equipment performance between laboratories
A JG Summit Company
ISO 9001: 2000

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Staffing & Responsibilities

Chemist (1):
Unit Technical Support and Problem Solving Analytical Method Development and Commissioning Analytical Method Trouble-Shooting Interface With R&D Programs

Supervisor (1):
Day to Day Operation of the Lab Personnel Administration Interface With Production (Sample Priorities, reruns, Etc.) Quantity and Quality of QC Data Budget Responsibility Technician Training
A JG Summit Company
ISO 9001: 2000

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Staffing & Responsibilities

Technician (4 Shifts, 1 per shift, & 2 Day):
Quality Control Testing (Determine & Report) Calibrate Lab Equipment Note: Based on 2 Reactor / 2 Extruder System

Quality Coordinator:
Production Representative To R&D as it relates to Product Specifications, Quality Studies, Special Programs. Makes decisions of product disposition. Has final authority on rating product quality Receives Customer Complaints and coordinates resolution. Inputs on production and catalyst run plans.
A JG Summit Company
ISO 9001: 2000

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Laboratory Equipment
X-Ray Flourescence Spectrometer
Used for additive determination in polyethylene, as well as residual metals analyses.

Melt Index Plastometer

Used for determining melt flow properties. Can perform melt index both by the manual-cut-andweigh and automatically timed.

Fume Hood for Ash Analysis

A 20 gram sample is weighed into a platinum crucible, and placed on a bunsen burner to burn off the polymer portion. The residues remaining in the cubicle are catalyst residuals.
A JG Summit Company
ISO 9001: 2000

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Laboratory Equipment
Density Gradient Apparatus
Polyethylene specimens are compression molded and then cut into small shapes and dropped into a gradient filled with a solution of water and isopropanol. The specimen is then plotted against calibrated density floats already in the gradient solution.

Low Boy Film Extruder

Polyethylene resin, is placed into the hopper and extruded at prescribed conditions as specified for either low or high density material. After the sample is allowed to extrude for approximately 15 minutes, a sample resin is taken, and a numerical rating is assigned to the sample based on a set of Film Appearance Standards.
A JG Summit Company
ISO 9001: 2000

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Laboratory Equipment
Tape Extruder
Used to analyze polyethylene samples for gel determination. A tape, approximately 3.05 m long, 0.51 mm thick, and 38.1 mm wide, is collected and inspected for gels that are 0.80 mm or larger in size. A numerical rating is assigned and reported.

Bulk Density Apparatus

Used to measure the apparent bulk density of polyethylene in kg/m3.

Impco Blow Molding Machine (Bottles)

A parison is extruded into a set of molds, injected with air, cooled and formed into a bottle, ejected, then weighed and inspected for gel content.
A JG Summit Company
ISO 9001: 2000

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Laboratory Equipment
UV Spectrophotometer
Used for the determination of Irganox 1010, Irganox 1076, or BHT in polyethylene resin. An appropriate calibration curve of absorbance vs. additive content is used to determine the level of additive being added.

Hunterlab Colorimeter
A compression molded specimen is placed over the sample port and analyzed for a numerical value, based on CIE Color System Tri-stimulus Values X, Y, & Z, to the Union Carbide Corporation Color Rating.

A JG Summit Company
ISO 9001: 2000

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Laboratory Equipment
G. C. Head-Space Analyzer
Used to determine residual hydrocarbons in polyethylene. It is based on ASTM D4526, modified to correct for hydrocarbons dissolved in the resin, according to Henrys Law.

Inston Mechanical Tester

Used to determine tensile strength, elongation, and yield strength of polyolefins and other semi-rigid materials.

A JG Summit Company
ISO 9001: 2000

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Glossary of Terms
Amorphous
Refers to molecules that lie in a tangled state, or with very little order.

Branching
Side chains attached to the main chain of the polymer.

Brittleness
Refers to the test temperature at which plastics and elastomers rupture by impact under certain conditions.

Catalyst
A chemical substance added that speeds up the polymerization of a compound.

Compression Molding
A technique in which the molding compound is placed in an open mold cavity, the mold is closed, and heat and pressure are applied until the material has cured or cooled.
A JG Summit Company
ISO 9001: 2000

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Glossary of Terms
Cross-linking
The tying together of adjacent polymer chains.

Crystallinity
The measure of the ability of the molecules in the resin mass to orient themselves into ordered three dimensional arrays or arrangements.

Elongation
The distance that it takes to break a molded specimen (in %).

Extrudate
The product deliver by an extruder.

FDA
Federal Drug Administration

A JG Summit Company
ISO 9001: 2000

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Glossary of Terms
Fluorescence
A property of a substance that causes it to produce light while it is being acted on by radiant energy, such as ultraviolet light or x-rays.

Gloss
The measure of shininess of a plastic surface.

Hardness
The resistance of a material to compression, indention, and scratching.

Haze
The cloudy appearance of an otherwise transparent sample, caused by scattered light from within the sample or from its surface.

Hoppercar
Container for transporting resin
A JG Summit Company
ISO 9001: 2000

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Glossary of Terms
Impact Strength
The measure of the energy needed, or absorbed, in breaking a specimen.

Injection Molding
A molding procedure in which a heat-softened plastics is formed from a cylinder into a relatively cool cavity which gives the item the desired shape.

Linear
Refers to a long straight-chain molecule.

Melting Point
The point at which a solid melts

Molecular Weight
The sum of the atomic numbers of a molecule.
A JG Summit Company
ISO 9001: 2000

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Glossary of Terms
Molecular Weight Distribution
Used to describe the number of different sizes of polyethylene molecules in resin.

Moldability
The ability for molten polyethylene to form to a mold.

Permeability
The ability of a material to leak or pass through the wall made of resin.

Polymerization
The process of growing large molecules from smaller ones.

Relative Density
The density of a given substance divided by the density of water.

A JG Summit Company
ISO 9001: 2000

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Glossary of Terms
Shrinkage
The ability of a plastic to shrink around an object.

Stabilizer
An ingredient used in the formulation of plastics to assist in holding the physical and chemical properties of the compounded materials at their initial values throughout the processing and service life of the material.

Stiffness
The capacity of a material to resist a bending force.

Strain
The amount of deformation caused by stress.

Stress
The amount of pulling force applied to a material until it breaks.
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ISO 9001: 2000

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Glossary of Terms
Swell
Refers to the bottle weight

Tear Strength
The force to initiate tearing or the force to propagate a tear.

Tensile Strength
Refers to the pulling force required to break a molded polyethylene specimen.

Toughness
The energy required to break a material, equal to the area under the stress-strain curve.

Viscosity
A measure of the internal friction resulting when one layer of fluid is caused to move in relationship to another.

Warpage
The distortion of a flat surface, such as molding lids and boxes immediately after molding. A JG Summit
Company
ISO 9001: 2000