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Reinforcements
Fiber Reinforcements Glass Fibers Carbon/Graphite Fibers Organic Fibers Boron, Silicon Carbide, and Specialty Reinforcements Fabrics and Other Reinforcement Forms Particle and Whisker Reinforcements Reinforcement/Matrix Interactions Comparisons of Reinforcements
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Objectives
Understand the differences and similarities in major types of reinforcements used in composite structures Identify the principal uses for each of the major types of reinforcements. Discuss the principal methods for manufacturing reinforcements Compare the different types of reinforcement forms and evaluate their relative merits.
Fiber Reinforcements
Reinforcements for composites can be
Fibers, Particles, or whiskers Each has its own unique applications, although fibers are the most common in composites. Particles and whiskers improve slightly the stiffness (modulus) and reduce the CLTE of the base resin, but decrease the strength and impact.
Fibers are materials that have one very long axis compared to others and is characterized by the aspect ratio (fiber length divided by fiber diameter)
Length of short fiber = 3 mm, diameter = 12.7 microns (10-6 m) Length of long fiber = 6 mm, diameter = 10 microns (10-6 m) Aspect ratio = 3/12.7 x 1000 Fibers are stronger in the length direction than in the cross direction
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Fibers
Fibers are produced by drawing the fiber which is accomplished by physically pulling the solid but pliable (plastic) fiber in the long direction. Fig 3-1
This orients the molecules along the length of the fiber so that the tension load on the fiber pulls more against the molecular chains themselves than against a mere entanglement of the chains.
Tension pulling
Fibers
Fibers are available as Continuous or Discontinuous
Continuous can be in a variety of weaves, woven, mats, etc. Discontinuous can be chopped into lengths from 3mm, 6mm 12mm, and up to 25mm
Particles have no preferred orientation and have an irregular shape. Used to reduce cost, shrinkage, CLTE
Glass Fibers
Fiber reinforcements have been known and used for centuries.
Renaissance Venetian artisans incorporated glass strands in crossed or web-like configurations to strengthen their fine, thin walled glass objects, e.g., vases, etc..
Two processes
Marble process where the glass ingredients are shaped into marbles, sorted by quality, and then remelted into fiber strands Alternatively, the molten glass is introduced directly to fiber strands.
The glass melt flows through formation bushings and then air cooled
Continuous strands are called filaments. Diameter is controlled by hole size, draw speed, temperature, viscosity of melt, and cooling rate. Protective coating or SIZING is applied so that the fibers pass through the mechanical equipment without breaking. Fibers are elongated or drawn and then wound up in rolls or tows.
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Glass Fibers
Types of glass fibers
Glass is an amorphous material that consists of a silica (SiO2) backbone with various oxide components to give specific compositions and properties. Several glass fibers can be produced, but only 4 are used. Table 3-1
E-glass: electrical glass Ca aluminoborosilicate composition with max 2% alkali Most common glass for composites and used when strength and high electrical resitivity. Lowest cost glass S-glass: high strength glass and S2 40% higher strength and better property retention at high temp Used in advanced composites and aerospace applications C-glass: chemical resistant glass Has soda-lime borosilicate composition and due to its chemical stability is used in corrosive environments Quartz: Used for electrical applications where a low dielectric material is required, e.g., antennas and in radomes
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Glass Fibers
Properties of Glass Fibers: (Table 3-1)
Property Density Tensile Strength, ksi Tensile Modulus, Msi CLTE (in/in/ F) x10-6 Specific Heat @72F Softening Point, F Dielectric Constant Chemical Resistance (% wt gain after 24hrs) In H20 In 10%HCl In 10% H2SO4 In 10% Na2CO3 Type of Glass C E S 2.49 2.54 2.48 460 500 665 10 4 0.2 1381 0.008 10.5 2.8 0.195 1550 0.002 12.4 3.1 0.176 1778 0.003
Chemical coating (sizing) is added to protect the fibers and holds the individual filaments together.
Usually the sizing agent is temporary and a finish (PVAc with organo-silane coupling is added after the size is removed
The sizing agent (size) can be a finish as well. Coupling agent are molecules
One end that is compatible with the silane structure of the glass The other is compatible with the matrix resin. Different coupling agents can change strength values 100%
Antistatic agents and lubricants can be added to match the desired use of glass as a chopped glass or woven mat.
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Compression Molding
Compression molding was specifically developed for replacement of metal components with composite parts that are produced at fast cycle times (less than 60 seconds)
The molding process can be carried out with either thermosets (SMC, BMC, rubber) or thermoplastics (GMT- Glass mat thermoplastic). However, most applications today use thermoset polymers. In fact,compression molding is the most common method of processing thermosets.
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Continuous fiber
Filament winding
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Discontinuous: Roving form that can be sprayed into a 3-D preform Continuous: Roving form that is woven into a glass sheet and then formed to shape (preform)
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Processing of Composites
Glass or Carbon Fiber are in Continuous Preform Sheet and molded with Open Mold processes
Vacuum bag, pressure bag, SCRIMP
autoclave: Apply Vacuum Pressure and Heat in an oven which can be 5 feet to 300 feet long Copyright Joseph Greene 2001 17
Properties of Materials
Tensile modulus
Low alloy steel Aluminum Carbon fiber Glass fiber Aramid fiber (Kevlar) Low alloy steel Aluminum Carbon fiber Glass fiber Aramid fiber (Kevlar) 207GPa(30Mpsi) 72GPa (10Mpsi) 300GPa(40Mpsi) 76GPa (10Mpsi) 125GPa (20Mpsi)
Density
Spec Mod
7.85 g/cc 26spGPa 2.8 g/cc 26spGPa 1.8 g/cc167spGPa 2.56g/cc 30spGPa 1.4g/cc 89spGPa
Tensile strength
1500MPa(220Kpsi) 500MPa(75Kpsi) 2400MPa(360Kpsi) 2000MPa(300Kpsi) 3000MPa (450Kpsi)
Density
Spec Str
7.85 g/cc 191spMPa 2.8 g/cc 178spGPa 1.8 g/cc4320spGPa 2.56g/cc 781spGPa 1.4g/cc 2140spGPa
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hoods
Sheet Molded Compound (SMC) with compression molding: Camaro, Firebird, Corvette, Ford trucks Polyester resin and glass mat preform with Resin Transfer Molding (RTM): Viper, Heavy duty trucks)
bumper beams
Glass Mat Thermoplastic (GMT) with compression molding : Camaro, Firebird, Venture, Transport,
Interior
floor pan
Polyester resin and glass mat preform with Resin Transfer Molding (RTM): Corvette
Engine
Sheet Molded Compound (SMC) with compression molding: valve covers, intake manifolds, fluid containers, etc.
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SMC
Sheet Molding Compound: Polyester Resin and chopped glass
8-25 -98
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SMC
Sheet Molding Compound
SMC
Sheet Molding Compound
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Marine Applicactions
water skis, water crafts, snorkel equipment, fishing gear diving equipment, submersibles, hovercraft, mine sweepers, canoes, kayaks
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Carbon/Graphite Fibers
Need for reinforcement fibers with strength and modulii higher than those of glass fibers has led to development of carbon Thomas Edison used carbon fibers as a filament for electric light bulb High modulus carbon fibers first used in the 1950s Carbon and graphite are based on layered structures of hexagonal rings of carbon Graphite fibers are carbon fibers that
Have been heat treated to above 3000F that causes 3 dimensional ordering of the atoms and Have carbon contents GREATER than 99% Have tensile modulus of 344 Gpa (50Mpsi)
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Carbon/Graphite Fibers
Manufacturing Process
Current preferred methods of producing carbon fibers are from polyacrylonitrile (PAN), rayon (regenerated cellulose), and pitch.
PAN
Have good properties with a low cost for the standard modulus carbon High modulus carbon is higher in cost because high temperatures required
PITCH
Lower in cost than PAN fibers but can not reach properties of PAN Some Pitch based fibers have ultra high modulus (725 GPa versus 350GPa) but low strength and high cost (Table 3-2)
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Carbon/Graphite Fibers
PAN Manufacturing Process Figures 3-3 and 3-4
Polyacrylonitrile (PAN) is commercially available textile fiber and is a ready made starting material for PAN-based carbon fibers Stabilized by thermosetting (crosslinking) so that the polymers do not melt in subsequent processing steps. PAN fibers are stretched as well Carbonize: Fibers are pyrolyzed until transformed into all-carbon
Heated fibers 1800F yields PAN fibers at 94% carbon and 6% nitrogen Heated to 2300F to remove nitrogen yields carbon at 99.7% Carbon
Carbon/Graphite Fibers
PITCH Manufacturing Process Figure 3-3
Pitch must be converted into a suitable fiber from petroleum tar
Pitch is converted to a fiber by going through a meso-phase where the polymer chains are somewhat oriented though is a liquid state (liquid crystal phase) Orientation is responsible for the ease of consolidation of pitch into carbon
Stabilized by thermosetting (crosslinking) so that the polymers do not melt in subsequent processing steps Carbonize: Fibers are pyrolyzed until transformed into all-carbon
Heated fibers 1800F Heated to 2300F
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Improvements in the elastic (Youngs) modulus by treating the carbon fibers at higher temperatures resulted in a lower ILSS values.
Low values = poor bonding between the carbon fiber and the matrix resin.
Surface treatments are needed to improve the fiber/matrix interfacial bonding and consequently the ILSS Oxidative surface treatments using liquid phase and not gaseous phase
Drawing the fibers through a bath of some convenient oxidizing agent nitric acid, potassium peranganate, sodium hypochlorite Drawing the fibers through an acidic or alkaline electrolytic bath (preferred) Result of oxidation is to clean the carbon surface and then to attach chemical groups, hydroxides, which can Joseph bond Greene with the matrix or sizing agent Copyright 2001
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Tensile modulus and tensile strength are determined by using either a single fiber or a strand of fiber filaments.
Statistical methods are used because of erratic data from single fibers Testing conditions and processing parameters affect properties, Length of fiber specimen increases then more flaws are possible in the fiber and reducing strength. Not affected by strain rate or testing temperature. Heat treatment temperature, time, stretch, type of precursor, surface treatment
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Series1
Series2
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Carbon fibers have very low CLTE, slightly negative (contract upon heat)
CLTE becomes more negative with increasing modulus. The contraction can be combined with a positive CLTE of a polymer matrix to have a net zero CLTE.
Mechanical Properties
Ideal engineering material would have high strength, high stiffness, high toughness, and low weight. Carbon fibers combined with polymer matrices meet these criteria more closely than any other material Carbon fibers are Elastic to failure at normal temperatures Creep resistant and nonsusceptible to failure. Chemically inert except in strong oxidizing environments or in contact with certain molten metals. Excellent damping characteristics.
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Brittle and low-impact resistance, Low break extensions (low strain to failure), Low compressive strengths and small CLTE Expensive compared to glass fibers Aircraft control surfaces- wing spoilers, flaps, elevators, rudders Helicopter rotor blades and aircraft landing gear and doors, Transportable bridges Automotive drive shafts and leaf springs and structural beams Sporting goods: golf clubs, tennis racquets, fishing rods, skis, frames Racing car bodies, spacecraft, rockets, missiles Thermal applications
Heat shields for missiles and rockets Aircraft brakes and aerospace antennas and space telescope platforms
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Applications
Electrical conductivity
Shield against radio frequency interference (not s good as metal) Touch switches
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Organic Fiber
Most common organic fiber used for reinforcement
Aramids, with Kevlar, a DuPont fiber as a major brand Other aramids Ultra high orientation polyethylene fiber (Spectra)
Aramid
Introduced in 1971 in commercial products. Used for reinforcements for tires, belts, and other rubber-related goods Bullet proof vests, high strength cloth, sails for racing boats.
Manufacturing Process
Para-phenylene diamine and terphthaloyl chloride are mixed in an organic solvent to form Para-phenylene-tere-phthalamide (Aramid)
Fig 3-5 is the chemical reaction- condensation reaction Highly aromatic nature of polymer gives good thermal and strength properties and linear nature of the bonding and hydrogen bonding gives good rigidity.
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Note: The fibers are not drawn to increase orientation of the molecules, unlike normal textile fibers and glass fibers.
Aramid fibers are oriented in the solution and during spinning are further orientated as it passes through the spinnerette
No surface treatment is applied as with caron fibers. A finish or size (usually epoxy) is applied for many applications, especially for weaving, making rope, and ballistic reasons, though not for composites Bundles of filaments range from 134 to 10,000 filaments per bundle.
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Property difference is due to changes in process conditions which promote additional crystallinity in the high modulus and ultra modulus Tensile strength and modulus of aramids are much higher than other organic fibers, though not as high as carbon fibers. Aramid fibers are less brittle than carbon or glass fibers Failure mode of aramid fibers is breakage into small fibrils which are like fibers within the fibers.
Tensile failure initiates at the end of the fibrils and is propogated by shear through the fiber. The provides very high tensile strengths for aramid composites, but low compression strengths which are 50% of carbon fiber composites
Aramid fibers are flame resistant and resistant to most solvents except strong acids and bases.
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Kevlar are hygroscopic and are susceptible to moisture and need to be dried Aramids do not bond well to matrices as do glass and carbon fibers
The ILSS (interlaminar Short beam shear) values are lower.
Properties of Kevlar 29 Tensile Mod MPa (psi) 83 (1,200) Tensile Strength MPa 3.6 Elongation % 4 Density g/cc 1.44 Kevlar 49 131 3.6 2.8 1.44 149 186 3.4 2 1.47
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Leading edges of wings and other structures where impact damage might be expected. Pressure vessels
Approximately the same strength and modulus as Aramid Higher specific modulus and strength due to low density Solvent resistant superior to aramid Thermal resistance is less than aramid
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Boron and Silicon carbide (SiC) are the most common of very high modulus reinforcements
Developed in the 1960s at Texaco and United Tech Principal use of
Boron is as a reinforcement with epoxy SiC as a reinforcement in ceramic and metal matrices
Manufacturing method
Made by Chemical Vapor Deposition (CVD) Fig 3-6 A substrate filament, e.g., Tunsten for Boron, and Carbon for SiC Is pulled through a cleaning solution Deposition chamber T=2500F: Chemical reaction occurs on the surface of the heated filament. Boron has trichloride and hydrogen SiC reactants are alkyl silanes with Si-C-Si structure and hydrogen Boron fibers are 4 to 8 mils in diameter SiC fibers are 5 to 6 mils. Fibers are wound onto spools Boron fibers are consolidated with epoxy for prepreg uni tape or Al foil
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Boron and SiC have very high modulus and strength Crystal structure
Boron is small crystals
Amorphous
SiC has
larger crystal structure
Boron fibers have high modulus due to swelling of Tungsten filament when reacting with boron trichloride
Surface structure is scale-like or corn-cob appearance
SiC has excellent high temp properties due to SiC not reacting with the carbon. Especially important in metal matrix composites where reinforcements may be subjected to molten metal. Copyright Joseph Greene 2001
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SiC has a surface that can be modified by changing the fabrication method to improve bonding with specific metals. Uses
Aerospace and consumer markets for medium to high temperatures 600-900F (315480C)
Specialty Fibers
Carbon fibers with fluorine for CF fibers for electrical Al fiber with high modulus as Al reinforcement for radar evade Nitrides resist thermal shock and CLTE is less than Al
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Types of reinforcements
Fibers: general term for material with a long axis (length) that is many times greater than its diameter Filament: A single fiber that is formed by a single hole in the spinning process. Strand: Bundle or group of untwisted filaments Tow: Untwisted bundle of continuous filaments usually with a specific count, e.g., 12,000 filaments or 48K Roving: Number of yarns or tows collected into a parallel bundle without twisting. Tape: Collection of parallel filaments that are held together with a resin (binder) matrix. Yarn: Twisted bundle of continuous filaments or twisted tow. Woven fabric: Planar material made by interlacing yarns or tows in various specific patterns. Braiding: Interlacing of yarns or tows into tubular shape instead of flat fabric. Mat: Sheet-like material consisting of randomly oriented chopped fibers or swirled fibers held together loosely by a binder
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Weave types
Plain weave is the simplest: interlacing yarns: one over & one under. One warp (machine direction) and one fill yarns.
Very Stable weave and most resistant to in-plane stresses. Stiff weave with good resin flow and good air removal. Used for flat laminates, printed circuit boards, narrow fabrics, molds, and covering wood boats.
Basket weave is similar to plain weave, except that two warp yarns are woven as one over and under two fill yarns.
Less stable and more pliable. Flatter and stronger than plain weave.
Crow-foot satin weave has one warp yarn carried over 3 then under 1 fill yarn.
Improved directional properties with more strength in one direction than plain weave More pliable and can comply with complex shapes and contours. Used for fishing rods, diving boards, skis, aircraft ducts, channel, and conduit.
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Leno weave is produced by having two parallel warp yarns twisted around each fill yarn, providing a locking effect.
Reduces distortion of low count, open weave fabric Provides heavy fabrics for rapid build-up of plies. Used as inner core for support of thin coatings for tooling and repairs. Have excellent drape and can be purchased with 45
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Interphase theory
Recognition of a flexible, 3-D interphase network which is thought to exist between reinforcement and matrix resin.
Polymer network formed by coupling compound or the amount into which the resin can penetrate.
Adhesion theory
Predictions of bond strength between matrix and reinforcement can be obtained by applying principles of surface chemistry.
Bonding is dependent upon the surface energy of the matrix and the fiber and air Surface energy: energy necessary to move a molecule from the bulk to surface. If surfaces are a liquid and a vapor it is called surface tension.
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Comparisons of Reinforcements
Table 3-5
Material Steel Titanium Aluminum Glass Fiber Carbon Fiber Aramid Fiber Boron Fiber SiC Fiber Density 7.8 4.5 2.8 2.5 1.9 1.4 2.6 3.5 Ten Strength Sp Ten Strength Ten mod Sp Ten Mod ksi Msi 145 18.6 29.0 3.7 134 29.8 16.0 3.6 67 23.9 10.0 3.6 246 98.4 10.0 4.0 228 120.0 55.0 28.9 385 275.0 19.0 13.6 443 170.4 23.0 8.8 500 142.9 57.0 16.3
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