Chapter 5.

Introduction to Polymer Composite Processing

Hatsuo Ishida NSF Center for Molecular and Microstructure of Composites (CMMC) Department of Mascromolecular Science Case Western Reserve University Cleveland, Ohio 44106-1712 51. Introduction

5.2. Advantages of Composite Materials 5.3. Brief Overview of Major Composite Processing Methods 5.3.1.Hand lay-up Molding 5.3.2.Spray-up Molding 5.3.3.Compression Molding, Transfer Molding, Resin Transfer Molding 5.3.4.Injection Molding, Plunger-type Injection Molding 5.3.5.Reaction Injection Molding 5.3.6.Pultrusion 5.3.7.Filament Winding 5.4. Classifications and Definitions of Composite Materials 5.5. Surface Treatment of Reinforcement Materials 5.5.1.Cost Factor 5.5.2.Chemistry of Surface Treatment and Interfacial Structure A. Glass Fibers and Inorganic Fillers B. Carbon Fibers C. High Modulus Organic Fibers 5.6. Selection of Materials 5.7. Selection of Processing Methods 5.7.1.Aspect Ratio 5.7.2.Shape of the Final Product 5.7.3.Time Necessary to Form Hard Solid 5.8. References

Chapter 5. Introduction to Polymer and Composite Processing

5.1. Introduction Polymers are generally produced as powders, pellets, and liquids. In order to produce polymeric products with desired shapes, thermoplastics must be melted and cool to a final product shape whereas thermosetts must undergo further polymerization to complete crosslinking reactions to finally solidify into the designed shape. These operations are called processing. Many factors influence the processing operations. Those include viscosity, orientation of heterogeneous phases, rate of reactions, and volatile formation. Among these factors, the viscosity consideration is by far the most dominant factors in processing. Viscosity is strongly influenced by temperature, share rate, molecular weight and its distribution, molecular structure of the polymeric chains and heterogeneity of materials. Thus, the study of flow behavior of polymeric materials, which is called rheology, is very important in understanding the proper conditions for processing. A composite is a heterogeneous substance consisting of two or more materials which does not lose the characteristics of each component. This combination of materials brings about new desirable properties. Naturally occurring composites include tendon, bone, bamboo, rock, and many other biological and geological materials. For composite engineering applications, we restrict ourselves to synthetic polymer matrices which are used with naturally occurring mineral fillers such as wollastonite, silica, mica, and calcium carbonate, and synthetic fibers like glass fibers and carbon fibers. In the subject of composite processing, we will learn how to make the best use of these available materials through the understanding of chemical interaction of ingredients, structural changes during processing, suitable processing methods for desired product shapes and the resultant consequence on the mechanical and physical properties. Therefore, we will deal with interdisciplinary subjects including rheology, chemistry, mechanics, machinery, and sometimes, economy. 5.2. Advantages of Composite Materials Composites have many engineering advantages over synthetic polymers and copolymers. Some of these advantages are: i. Reinforcement of the resin resulting in increased tensile strength, flexural strength, compression strength, impact strength, rigidity and combination of these properties. ii. Increased size stability. iii. Improved fire retardancy. iv. Corrosion protection. v. Improved electrical properties; reduction of dielectric constant. vi. Coloring. v. Improved processibility; controlled viscosities, good mixing, controlled orientation of fibers.

One of the most important properties composite materials offer is the strength per density or modulus per density termed as specific strength and specific modulus, respectively. For transportation applications including aerospace applications, the weight of the vehicle is a critical importance for energy saving and payload increase. Those materials used for polymer-matrix composites have usually much less density than metallic materials, thus specific properties often far exceeds that of matellic parts. Figure 1.1 illustrates the specific strength and specific modulus of typical materials. Specific tensile modulus (GPa/g/cm3 ) 300

200

Carbon (P120)

Carbon (T1000) Boron

100

Carbon (T300) Alumina SiC Aramid (Kevlar 49) S-glass

Aluminum

Steel

E-glass

1 2 Specific tensile strength (GPa/g/cm 3 )

Figure 1.1. Specific tensile modulus versus specific tensile strength of various materials. Properties are those of fibers. 5.3. Various Processing Methods In many cases, polymer composite processing utilizes the same technique as polymer processing which include injection molding, compression molding and extrusion. There are other techniques which are unique only to polymer composite processing. These include filament winding, pultrusion, and hand lay-up. In spite of the fact that some techniques are used commonly with polymer processing, the operational conditions can be very different; thus, it is important not to directly transfer knowledge without careful consideration. In this section, a brief explanation of various processing methods will be given. 5.3.1.Hand Lay-up Molding Hand lay-up molding is the method of laying down fabrics made of reinforcement and painting with the matrix resin layer by layer until the desired thickness is obtained. This is the most time and labor consuming composite processing method, but majority of aerospace composite products are made by this method in combination with the autoclave method. Due to the hand assembry involved in the lay-up procedure, one can align long fibers with controlled orientational quality. Another advantage of this method is the ability to 3

accommodate irregular-shaped products. Such advantages are utilized in low performance composites including fiber-glass boat and bath tub manufacturing.

Brush Reinforcement

Mold

Figure 1.2. Schematic diagram of hand lay-up operation. 5.3.2.Spray-up Molding

Spray-up booth

Spray-up gun

Mold

Glass roving

Resin

Catalyst

Figure 1.3. Schematic diagram showing spray-up operation Spray-up molding is much less labor intensive than the hand lay-up method by utilizing a spray gun and a fiber cutter. However, only short fiber reinforced composites can be made. A 4

continuous fiber is fed into the cutter and chopped. The chopped fiber is sprayed upon a mold with the stream of resin mist and catalyst delivered through separate nozzles. The sprayed mixture of fiber and resin soon cures on the mold at room temperature and the product is produced. Because of the spraying operation, large and complex-shaped objects can be easily made. 5.3.3.Compression Molding, Transfer Molding and Resin Transfer Molding Compression molding uses a press to compress either a dough of resin and fiber mixture, or the layers placed by a hand lay-up method or mechanical means, typically at an elevated cure temperature. With the compressive force, the void content is lower than the ordinary atmospheric pressure processing method.

Matched metal die Composite material

Platen

Hydraulic press Figure 1.4. Schematic diagram of a compression molding press A matched die mold allows shaping of the composite precursor into reproducible shapes. Although a compression molding machine is used, it is still a labor intensive method as the dough or layed-up materials must be weighed and hand-fed into the mold. Transfer molding is the improved version of compression molding from the material metering point of view as the fiber/resin mixture is transfered from the reservoir into the mold cavity by the press. However, a long-fiber reinforced composite cannot be made. This method is nearly identical to a plunger-type injection molding operation based on the material flow. The term "transfer molding" is used for a compression press operation while plungertype injection molding is obviously carried out in an injection molding machine. Resin transfer molding is the same as the ordinary transfer molding except that only the resin is transfer molded into the mold cavity where fabrics are placed beforehand. Preforms of glass fibers and other reinforcements can be made with short fibers and sometimes continuous fibers. Preforms must be made to withstand the pressure of resin injection in order to avoid compression of the fibers during mold filling which would lead to inhomogeneous fiber distributions in the final part. Curing proceeds typifcally after filling at an elevated temperature. 5

5.3.4.Injection Molding Injection molding is probably the most extensively used method for processing short-fiber reinforced thermoplastics. The fiber/resin mixture, whether it is preblended or fed as a physical mixture, is fed into the hopper and transfered into the heated barrel. The material softens by the heat transfer from the barrel wall. At the same time, the screw rotates to apply high-shear process to further heat the material and fill the barrel. The molten material is collected in front of the screw by the rotation of the screw, and then injected with a high pressure into the mold cavity through the runner and the gate. The mold is cooled below the solidification temperature of the resin in case of thermoplastics composites. The level of automation of this method is the highest among many processing methods. Due to the intensive mixing with high-shear and passage through a narrow gate, extensive fiber damage occurs, therefore, injection molding for composite materials is suitable only with short fiber reinforced or particulate-filled polymers. Hopper Mold Composite Material

Screw

Barrel Figure 1.5. Schematic diagram of an injection molding machine There is a critical length of fibers below which the fiber length does not degrade. The critical length is determined by the rheological properties of the composite mold, fiber properties and instrument factors. Less fiber damage occurs when a plunger-type injection molding machine is used rather than a screw-type injection molding machine. Because the plunger-type injection molding machine does not achieve a high degree of mixing in the machine, the raw materials must be thoroughly mixed prior to feeding. 5.3.5.Reaction Injection Molding Reaction injection molding (RIM) is one of the newest processing methods. Instead of using already polymerized materials as matrices, highly reactive monomeric or oligomeric ingredients are placed in two tanks which are then quickly mixed by impingement, and injected into the mold cavity. As soon as the two materials are mixed, chemical reaction begins to form a polymeric matrix, which completes typically within 5-30 seconds. Thus, the major portion of the RIM machine is a high pressure pump and a metering system. Again, with high intensive shear, only short fibers and fillers can be used as reinforcements. However, RIM utilizes low viscosity chemicals and this allows the preplacement of continuous fiber-woven fabrics in the mold in the same manner as resin transfer molding. Distinction is made between these two methods based on the preparation of the resin precursor. When the resin formulation is already made, the method is called resin transfer molding while if the resin is prepared in-situ by an impingement or static mixer, the method is termed RIM.

Chemical A Chemical B

Mold

Impingement mixing head

Figure 1.6. Schematic diagram of a reaction injection molding machine. 5.3.6.Pultrusion Pultrusion is used only for polymer composite processing. A bundle of fiber rovings is passed through a wet resin bath, squeezed into a desired shape, passed through a heated die, and cured into a final composite. The solidified composite, typically reinforced unidirectionally with continuous fibers or sometimes bidirectionally, is pulled by a puller to continuously feed the uncured portion of the wet fibers into the hot die, thus the name, "pultrusion". This is one of very few continuous processing methods for continuous fiber reinforced composites. Only constant cross-sectional products can be made; the shape of the cross-section does not necessarily have to be the same, however. Roving Eyelet Heated die Puller Cut-off saw

Resin bath Figure 1.7. Schematic diagram of a pultrusion machine. 5.3.7.Filament Winding Filament winding is also a unique processing method for polymer composite processing with a continuous reinforcing fiber. Resin-wet rovings are wound with a certain pattern 7

around a mandrel. The wound mandrel is then placed into an oven and cured to a solid composite. Due to the controlled tension, squeezing action and controlled winding pattern, the fiber content can be very high to produce composites with one of the highest mechanical properties. The winding process is time consuming and is the cause of low productivity. However, due to its very high mechanical properties with automated operation, it is actively evaluated by aerospace industries. Motor Mandrel Roving Eyelet Resin bath

Figure 1.8. Schematic diagram of a filament winding machine. 5.4. Classifications and Definitions of Composite Materials The term reinforced polymer is often used for composites with fibrous materials while filled polymer is the description used for polymers with particulate fillers. Examples of the reinforced polymers are fiber-glass reinforced polyesters and carbon fiber reinforced polyimides. A vast number of filled polymers are used today, including calcium carbonate filled poly(vinyl chloride), clay-filled polyethylene and carbon black-filled polybutadiene. The role of fibers is relatively obvious and simple; reinforcing the strength of weak polymers. The properties tend to be anisotropic. However, fillers have complex roles and many of them are interactive. Some are added to homogeneously increase modulus and strength, and others are for dimensional stability, viscosity control, increased hardness, pigmentation, and even for cost reduction. Fillers do not necessarily lead to overall improvement of properties, and thus the role of added fillers must be carefully examined prior to use. For example, calcium carbonate is often added to unsaturated polyester resin for cost reduction, rheology control, and dimensional stability, but in sacrifice of the strength. Reinforced composites can be further classified into high-performance composites like filament wound plastics with glass fibers, or carbon fiber reinforced high temperature polymers made by hand lay-up method; and low-performance composites such as injection molded bulk molding compound (BMC) or composites made by the spray-up method. Extremity of the performance, whether it be the strength or use temperature, is the key factor for high performance composite. In general, high-performance composites tend to use a high fiber content as the mechanical and physical properties of reinforcing fibers are generally much greater than the matrix resin. Filler is a term used for materials other than continuous fibers and, in general, implies that the reinforcement effect is rather low. Fillers may be particulate or fibrous but the size is usually less than a millimeter. For the reinforcement effect of fillers, the aspect ratio, i.e. the

length-to-diameter ratio, is a critical importance. Extender is the word used for a filler which has almost no reinforcement effect and is used simply to reduce the amount of a plastic required. A hierarchy exists in the terminology of reinforcing fibers. The thinnest component is a filament whose diameter is typically between several micrometers to several tens micrometers. A few hundred to few thousand filaments are bundled together, which is assisted by a film former, to form a strand. Finally, many tens of strands make up a roving. When good mechanical properties are maintained in the temperature range around 150 oC, the polymer is called an engineering plastic. Nylon, polycarbonate, poly(ethylene terephthalate) and epoxy all belong to this category. Sometimes the term super engineering plastic is used to indicate polymers with further elevated use-temperatures above 200 oC. These include polyimide, poly(aryl ether ether ketone) and poly(phenylene sulfide). 5.5. Surface Treatment of Reinforcing Materials 5.5.1. Cost Factor Surface treatment is done to improve the adhesion of fillers and fibers to matrix resin by modifying the surface of the solid. Often, chemical structure and sometimes topology of the surface change upon the treatment. Those techniques used include chemical, plasma, corona discharge and flame treatments. When cost reduction is the major goal of a change in fabrication, surface treatment of a filler is not a viable option. This point may be clarified by the following example. As of 1981, a certain polyethylene was priced $ 0.30/lb while typical untreated fillers were $ 0.05/lb. The cost of mixing the filler into the resin was about $ 0.07/lb. Hence, the higher the filler content the lower the cost of the composite. However, once the filler was surface treated, the unit cost went up to about $ 0.20 - 0.25/lb. When combined with the mixing cost, there is essentially no economic advantage. The economic factor is often ignored in the academic institution. However, it is one of the most essential motivations for manufacturing composites in today's industries and without understanding this point, a true grasp of composite processing cannot be achieved. 5.5.2. Chemistry of Surface Treatment and Interfacial Structure

A. Glass Fibers and Inorganic Fillers Inorganic materials like glass fibers and many fillers have poor compatibility at the fiber/matrix or filler/matrix interface. In order to improve adhesion at the interface, compounds with dual property, i.e. molecules having chemical functionalities similar to the fiber and the matrix resin, are used. Due to the coupling action of the fiber and the resin by the compatibilizing compound, this type of compound is often referred to as a coupling agent, such as a silane coupling agent. In addition to the adhesion promotion, coupling agents aid in protecting fiber surfaces and prevent inhibition of polymerization by the solid surfaces. A small amount of a coupling agent can often dramatically improve the mechanical and physical properties of composites. A typical loading level of coupling agent ranges from a small fraction of a percent to a few percent based on the weight of the fiber or filler. Other treatments such as plasma and corona discharge changes the chemical structure of the surface layers of fillers and fibers in an attempt to obtain similar compatibilization and adhesion promotion effects through chemical reactions. The coupling agent may be added to the filler as a neat liquid, an organic solution, or an aqueous solution. If a coupling agent is mixed into the filler/resin mixture, the treatment is 9

called the integral blending method. On the other hand, if a filler is separately treated, it is either termed as the dry blending method or the slurry treatment method. The dry blending method utilizes typically a small amount of a concentrated silane/organic solvent solution which is sprayed onto the tumbling fillers. Since the amount of the solution is small, and is an organic solution, the tumbling filler has an appearance of dry powder, thus the name dry blending method. The slurry method uses a large amount of a dilute silane solution, typically ofgr an gs aqueous solution, and the filler is in slurry form. 352 3940 [1 ]d 2860 DSt end 1 2 [27 249 320 700 1340 4640 1500 1920 1580 1820 1180 1680 2100 2560 6760 5580 6480 4420 4860 5340 5880 6380 6900 dL 5240 860 I [7 15 5580 5240 2040 5240 2220 2480 3180 3720 3540 4360 4440 4820 5280 5060 4160 4460 3800 5220 IDSt 29 1340 3500 580 960 40 [15 860 320 4640 1600 1980 1180 1340 1680 1540 1580 1440 1920 2380 2860 5220 6120 7300 5580 6480 4740 5180 5640 6160 6680 7220 4320 80 I5520] DSt 960 2 5240] 20 2480] 3360] 3940] 3540] 4320] 4360] 4580] 4620] 5060] 5240] 5220] 4820] 4460] 4200] 3500] 5520] Ar DSt [28 20 5520 1600 [9 chemdict I suspended 6480 IDSt 2840 1680 [16 3500 4580 1600 begin Ia 1440 DSt DSt 2480 SP [30 5520 grI 2 [0 5180 Ar DSt I 4640 4500 [17 5520 I 1860 4040 1920 DSt DSt [31 2560 5520 [1 I 5640 4040 IDSt 2 1600 [18 5520 2 Ar I 2480 238 DS /b

6 % userdict/chemdict L/gr/grestore L/tr/transform xl pp l SA RA}{6 -1 st}b/OrA{py -8 py np gs fill e o cp 5 a wy dp 0 In x w 0 2 bW dp/cY g -2 cw -1 CopyRight py 1 ChemDraw dp p cm fill pA sc -1 gr DA}{cw 8 m2 0 pp}{sqrt p 2 o 1 ix dv p l2 r lt{1 mv -9.6 -2 m 2 p s px sc mv cm 180 HA}{dL 0 gr}{pp}{gs -1 dp a}b/PT{8 sm o exec}{al s{dp dv m g dv mv dp rO dv o x -.6 WI py -1 sc exec sm 0 b2 neg lp st 12 xl wF np CA 5 p n 0 mv py 0 at p bd p LB sc 1.2 px gr neg 1986, m a}{ex 7 mv st p 2.25 e Laser 1 p l -9.6 m L/gs/gsave l arcn OA}{1 2 clip}b/Ct{bs p -1 gs ex pp aL p neg}if/py n l L/xl/translate cp np sl gr 0 at mv OB p wy m st}b/HA{lW l 12 0 o mv p 1 3.375 px 1 0 n/ex r 8 ro fill mv n gs 145 90 SA py 16.8 st}{0 np lp l 1987, 1 counttomark{bs Prep s wx ac sg OB/bL aR ix dp bW -1 bd px py sc e 0.3 gr ac px ro DA}{dL 0.6 rad 8 1 fill dict aL at 7 x m1 sc n 0 p cv SA dp end}b/Db{bs{dp DLB 0 eq{DD}{DS}ie py x -1 1 ey L/ie/ifelse Cambridge mt 1.2 gr p m bd ne{bW l 0 120 py 8 x dp rot -9.6 put sc m px DA}{cw m rO l}for m/w mv n/ey rad r -1 180 cm bW -1 ro 1.5 p 2 L/S{sf s p 0 b1 py g 0 CA ac chemdict 0 e dv tr/dy 0 1 l 0 -1 lt{-1 180 sm 21.6 bs 0 p st 2 SA -.6 aA a}ie}b/WW{gs x dp 5 0 a}ie}b/BW{wD py ac px 12 OA}{1 ne{bW 0 l dv}{bd}ie 5 sc np gr}{gs -1 dx rot p e st}{Asc cp L/ix/index m}b/dA{[3 DA}{dL s py m 8 p 6 Scientific 2.2 py m 0 1 x/dx 3 -8 g DLB 5 180 0 r n/dx l -1 g cm 360 a sc -1 2 lp sl dv px -1 0 16 begin/version gs 24.6 type[]type -1 p sqrt 2 4 12 r 2.25 neg}if/px ac gs p sm r arc x mv neg LB r py 0 dv/bd s gi 1 arc o 0 x sc s wF mv 2 0 OB 0 rO 180 0.5 SA CB dp 1 dy 3 gs al -4.8 st}{0 p Computing, 0 0.6 eq{DB}{DS}ie lW 90 L/l/lineto wD S]}b/dL{dA py SA gs e begin m ac 1 w l ac 1 cw pp DA}{2.25 CB 0.5 n/dy rev{neg}if sg 5 px 2 6 r x}if CA lp cW 2 1 sc DA}{cw 2.2 begin 16 px -1 25.8 rO eq{dp e dv -2 o -1 1 x fill sg m 0 py sg np s cX bs OA}{1 a setgray np[{py np 0 r x p wy p dp dv 24 r e fill gr 1 fill dv lp 16 lx 0 bW l mv s cv ne e L/mt/matrix lbs 0 0 o cm 0 wx rlineto cp cm 5 p def/b{bind 0 dp SA arc gr ac g/wb Inc. ly neg gr 0 sc}b/Ov{OrA 0 1 -1.6 n pp}{2 g o e -1 m l 0 rO 16 cm p p px w at sm 1 OA}{1.5 0 sm gs cY g 2 clippath gs ne{bW py sl l mv e sc ac l ac 3 2 eq{gs mt WI div x lp cm sm 27 1 ne 1.5 sc cm st cp px st}{Asc lW 4 m 270 0 bs cm e 1 bL s p ro gi gr}b/OB{/bS neg or{4 dup 1.6 0 fill}b/SA{aF sm w st}{px m py st p sm 0 2 SA l def}bind e L/mv/moveto SA dp tr 0 sm bd al cp p l fill AA}{1 p dv/bd gr put g/bb rO st cp py 27 DA}{270 e 1 wy st 2 l pp gs 1 l mv OA}{1 1 4 fill ZLB st}]e 0 rad neg 0 0.4 gr S r ac lW cm gr rO 0 g m 4.8 -1 a/py setgray o DT}]o 4 lt{pp 0 end px x -1 np setdash}d/c 1 px x}if o w 2 cpt gs dv ac 1 def/L{load sc p e sm}b/CB{n -1 39 wb eq{dL}if SA 25.8 xl dv m 0 p sc r}if -0.4 xl}{xl ap x x py 0.5 cp gr}b/In{ 0 round CA 2 e 1 sc px 0 l s 4 4 3 lW OA}{1 wx a 180 0 rad L/m/ at mv S}if/l 1 Bd pp g px st}{1 -1 g/cX ix ZLB lW DA} cv sg 1 py -0. m/ nH ex g pp ro} a/ gr p 3 0 1 w r 6 A 8 2 f e The chemical reaction of a coupling agent occuring during the treatment and drying of the filler is shown below using a silane coupling agent for example. currentpoint H2O RSi (OR') 3 RSi (OH) 3 + 3 R'OH Hydrolysis Organosilanetriol Adsorption

R HO Si O H O Si H Condensation Polymerization R OH - O - Si - O - Si - O O Si O Si currentpoint R

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Figure 1.9. Chemical processes during surface treatment of silaceous materials by a silane coupling agent. Regardless of the treatment methods, the silane loses its alkoxy groups and chemically reacts with the hydroxyl groups of the mineral surfaces. The reaction proceeds as follows. i. Dry Blending

The unreacted alkoxy groups will further react with the surface silanols or water on the filler surface. When the alkoxy groups are hydrolyzed, siloxane bonds between the silane molecules can be formed. Dry blending may be performed after prehydrolysis of the silane with a small amount of water added in the organic solvent, which leads to the similar chemical processes described in Figure 1.9.

10

386 4960 [1 ]d DSt gr [0 end 1[14 101 220 640 5880 1420 6080 1240 3160 1120 1580 2060 4900 5340 6240 6660 10 1580 II10 2300 2300 980 1020 2160 1380 1780 1980 1600 2340 2300 2380 2280 4200 28 2300 2540 460 880 40 5880 2220 5640 6840 1240 3160 1320 1820 2300 5160 5600 6040 6500 6920 1580 80 2540] DSt DSt 20 820] 2300] 2280] 1960] 1180] 1980] 2180] 1360] 2540] 2 [1 [16 20 Ar I 2220 chemdict /bs[[1 I 5600 2300 1 2540 220 begin DSt DSt 2300 [2 SP [17 15 980 I 6040 5640 2300] 2540 2280 DSt [18 [3 I I 6840 6500 2280 2540 DSt DSt [4 [1

%w userdict/chemdict L/gr/grestore L/tr/transform xl pp l SA RA}{6 -1 st}b/OrA{py -8 py np gs fill e o cp 5 a wy dp 0 In x 6 0 2 bW dp/cY g -2 cw -1 CopyRight py 1 ChemDraw dp p cm fill pA sc -1 gr DA}{cw 8 m2 0 pp}{sqrt p 2 o 1 ix dv p l2 r lt{1 mv -9.6 -2 m 2 p s px sc mv cm 180 HA}{dL 0 gr}{pp}{gs -1 dp a}b/PT{8 sm o exec}{al s{dp dv m g dv mv dp rO dv o x -.6 WI py -1 sc exec sm 0 b2 neg lp st 12 xl wF np CA 5 p n 0 mv py 0 at p bd p LB sc 1.2 px gr neg 1986, m a}{ex 7 mv st p 2.25 e Laser 1 p l -9.6 m L/gs/gsave l arcn OA}{1 2 clip}b/Ct{bs p -1 gs ex pp aL p neg}if/py n l L/xl/translate cp np sl gr 0 at mv OB p wy m st}b/HA{lW l 12 0 o mv p 1 3.375 px 1 0 n/ex r 8 ro fill mv n gs 145 90 SA py 16.8 st}{0 np lp l 1987, 1 counttomark{bs Prep s wx ac sg OB/bL aR ix dp bW -1 bd px py sc e 0.3 gr ac px ro DA}{dL 0.6 rad 8 1 fill dict aL at 7 x m1 sc n 0 p cv SA dp end}b/Db{bs{dp DLB 0 eq{DD}{DS}ie py x -1 1 ey L/ie/ifelse Cambridge mt 1.2 gr p m bd ne{bW l 0 120 py 8 x dp rot -9.6 put sc m px DA}{cw m rO l}for m/w mv n/ey rad r -1 180 cm bW -1 ro 1.5 p 2 L/S{sf s p 0 b1 py g 0 CA ac chemdict 0 e dv tr/dy 0 1 l 0 -1 lt{-1 180 sm 21.6 bs 0 p st 2 SA -.6 aA a}ie}b/WW{gs x dp 5 0 a}ie}b/BW{wD py ac px 12 OA}{1 ne{bW 0 ldv}{bd}ie 5 sc np gr}{gs -1 dx rot p e st}{Asc cp L/ix/index m}b/dA{[3 DA}{dL s py m 8 p 6 Scientific 2.2 py m 0 1 x/dx 3 -8 g DLB 5 180 0 r n/dx l -1 g cm 360 a sc -1 2 lp sl dv px -1 0 16 begin/version gs 24.6 type[]type -1 p sqrt 2 4 12 r 2.25 neg}if/px ac gs p sm r arc x mv neg LB r py 0 dv/bd s gi 1 arc o 0 x sc s wF mv 2 0 OB 0 rO 180 0.5 SA CB dp 1 dy 3 gs al -4.8 st}{0 p Computing, 0 0.6 eq{DB}{DS}ie lW 90 L/l/lineto wD S]}b/dL{dA py SA gs e begin m ac 1 w l ac 1 cw pp DA}{2.25 CB 0.5 n/dy rev{neg}if sg 5 px 2 6 r x}if CA lp cW 2 1 sc DA}{cw 2.2 begin 16 px -1 25.8 rO eq{dp e dv -2 o -1 1 x fill sg m 0 py sg np s cX bs OA}{1 a setgray np[{py np 0 r x p wy p dp dv 24 r e fill gr 1 fill dv lp 16 lx 0 bW l mv s cv ne e L/mt/matrix lbs 0 0 o cm 0 wx rlineto cp cm 5 p def/b{bind 0 dp SA arc gr ac g/wb Inc. ly neg gr 0 sc}b/Ov{OrA 0 1 -1.6 n pp}{2 g o e -1 m l 0 rO 16 cm p p px w at sm 1 OA}{1.5 0 sm gs cY g 2 clippath gs ne{bW py sl l mv e sc ac l ac 3 2 eq{gs mt WI div x lp cm sm 27 1 ne 1.5 sc cm st cp px st}{Asc lW 4 m 270 0 bs cm e 1 bL s p ro gi gr}b/OB{/bS neg or{4 dup 1.6 0 fill}b/SA{aF sm w st}{px m py st p sm 0 2 SA l def}bind e L/mv/moveto SA dp tr 0 sm bd al cp p l fill AA}{1 p dv/bd gr put g/bb rO st cp py 27 DA}{270 e 1 wy st 2 l pp gs 1 l mv OA}{1 1 4 fill ZLB st}]e 0 rad neg 0 0.4 gr S r ac lW cm gr rO 0 g m 4.8 -1 a/py setgray o DT}]o 4 lt{pp 0 end px x -1 np setdash}d/cR 1 px x}if o w 2 cpt gs dv ac 1 def/L{load sc p e sm}b/CB{np[{ -1 39 wb eq{dL}if SA 25.8 xl dv m 0 p sc r}if -0.4 xl}{xl ap x x py 0.5 cp gr}b/In{px 0 round CA 2 e 1 sc px 0 l s 4 4 3 lW OA}{1 wx a 180 0 rad L/m/mu at mv S}if/lp 1 Bd pp g px st}{1.0 -1 g/cX ix ZLB lW DA}{18 cv sg 1 py -0.4 m/aL nH exec g pp ro}ie}b a/px gr}b/ pp 3 0 1 w r 6 AA}{ 8 -2 2 fill exe lp gs 3 ix -1 def 1 36 rO 0 pp 4 n 24 o x o x sc 1 d a s g A p g x currentpoint R H O Si + R'O - Si - OR' O OR' Si currentpoint R R'O - Si - OR' + R'OH

19283746

Figure 1.10. Chemical reactions possible on a dry filler surface. ii. Prehydrolysis; Slurry Treatment This method leads to the chemical reactions described in Figure 1.9. If the surface is flat on the molecular level of the silane, thick multilayers can be easily formed. Although dry blending is a preferred method for a powdery filler because of the ease of drying, the alkoxy group of the coupling agent may not be completely hydrolyzed especially when the surface coverage is more than a monolayer. This results in small silane oligomers which are not chemically bound to the surface. This portion of the coupling agent, physisorbed silanes, migrates into the matrix resin during processing and modifies the structure of the matrix near the filler surface creating a region termed "matrix interphase" whose properties differ from the matrix bulk. The importance of this portion of the coupling agent has only recently been recognized and its roles are not fully understood. The addition of a small amount of water in the treating organic solution prior to the mixing helps the silane to hydrolyze more thoroughly. A fine particulate tends to form a cake which can be later crushed to reobtain a fine powder form. Therefore, the slurry treatment is usually avoided for this type of materials. Glass beads, coarse fillers or fibrous fillers are exceptions since they do not form hard cakes upon drying. Whenever permitted, wet treatment is preferred from the view point of environmental consideration. The concentration of aqueous treating solutions generally range from 0.05 to 2 % by weight. A further advantage of the wet treatment is that a more uniform surface treatment is achieved due to the abundance of the treating solution that can wet the entire surface of the filler or fibers. Also, the silane is hydrolyzed to an organosilanetriol. After the adsorption, the unstable silanetriols condense into the siloxane linkages forming large, crosslinked networks. Thus, the structure of the adsorbed silane is relatively insensitive to moisture compared to the dry blended silane. After the surface treatment, the reinforcements are usually dried at room temperature overnight followed by a heat treatment at an elevated temperature. A heat treatment at 110 oC for 5 to 30 min is typical. Too much curing of the coupling agent can be harmful and may lead to a loss of the organofunctionality. Industrially, the drying may be done immediately after the surface treatment by passing through an oven. In addition to the coupling agent, there are a number of ingredients in the so-called sizing agent including a lubricant, a film former, and an antioxidant. Detailed compositions are not disclosed other than in patent literatures. Figure 1.11 shows how the silane treatment can improve the dry and wet strength of fiberglass reinforced unsaturated polyester compared with the untreated glass fibers. The figure also shows the chronological progress of various coupling agents for polyester applications.

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Another useful function of the coupling agent is to increase bond permanence under hydrothermal degradation, and healing of the surface flaws of the fiber. Dry Strength Wet strength

600
Flexural Strength (MPa)

400

200

0 A B C D
Category

Figure 1.11. Progress in fiber-glass reinforced polyesters (from ref. 1). A: no surface treatment B: BJY treatment C: chrome complex D: vinyl-functional silane E: methacrylate-functional silane F: vinylbenzyl cationic silane Wet strength was measured after 2 h boil in water. Understanding the surface chemistry of reinforcements is very important when the function of the coupling agent is considered. A typical thickness range of the silane layers on a glass fiber surface is 1 to 10 nm as compared to the typical diameter of the glass fiber, 10,000 nm ( 10 m). In spite of its very thin layer, the structure of the silane layers on glass and metal surfaces has been under extensive investigation. Many monograms and review articles on the subject are available (2-7). Some of the major findings are listed below. i. Silanes adsorb onto a smooth surface such as a glass fiber as multilayers while a rough surface shows essentially a monolayer adsorption. This is due to the topological reasons influencing the orientation of the silane molecules (8).

ii. At the glass/silane interface as well as the silane/matrix interface, chemical bonds can be formed (9-11). iii. Within the silane multilayers, the molecules tend to form organized layers and the degree of organization depends on the flexibility of the organofunctionality (8, 12).

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iv. Silanes tend to adsorb head-to-head configuration because silanetriols form strong hydrogen bonds (12). v. Silanes preferentially adsorb onto the surface of fillers and change the surface energetics. As a result, the viscosity of the filler/resin system decreases dramatically by improved dispersion of the fillers (13, 14). Also, the catalytic effect of the fillers are inhibited by a thin film of silane (15), thus the inorganic fillers act as organic fillers.

vi. Silane interphase can intermix with resin matrix to form interpenetrating networks (16, 17). B. Carbon Fibers The surface treatment of carbon fibers is done quite differently from the aforementioned silane treatment of glass fibers because of the dissimilarity in surface functionalities. Carbon fibers are covered with the basal plane of graphite crystals, crystal edges of the graphite, and nongraphitic carbon. At the edge of the crystal, non-aromatic structures can exist including hydroxyl, carbonyl, and carboxylic acid groups (18-20). Typical example of the surface composition after a mild surface oxidation is 73% hydroxyl groups, 17% carboxylic acid groups, and 10% hydroxyl groups, while after an extensive oxidation it is 24% hydroxyl groups, 54% carboxylic acid groups and 22% carbonyl groups (21). Surface treatment of carbon fibers can be divided into two categories. Usually, the word surface treatment refers to the oxidative treatments on the carbon fiber surface. Those treatments include oxidation in a concentrated nitric acid, an electrochemical treatment, and a plasma treatment (22). The structural modification is usually confined within the layers very near the surface. The oxidative treatment increases the surface polarity and improves the adhesion with polymeric matrices. However, due to the increased polarity, the hydrothermal stability of carbon fiber reinforced composites is somewhat compromised. Another kind of surface treatment is referred to as a surface finish or a primer where typically a polymer or an oligomeric precursor of a polymer is coated on the fiber surface. This type of surface treatment is used for a protective coating as well as an interphase modifier (23). Although there is no clear definition of terminology, the word finish is used for a very thin surface coating while the word primer is used for a much thicker coating. In this context, the coating usually applied on carbon fibers is a primer. The thickness of the primer is usually in the range from 100 to 500 nm. Often used materials include epoxies and polyimides. C. High Modulus Organic Fibers Little is known on the surface treatment of high modulus organic fibers such as poly(para terephthalamide) (PPT) or gel processed polyethylene fibers. The typical method used is plasma treatment or corona discharge treatments of the fiber surfaces. Surface amination of PPT fibers has been studied (24): Improved mechanical strength of a PPT reinforced epoxy composite has been obtained by treating the PPT fibers in ammonium plasma at 50 W for 60 sec. This treatment introduced an amine functionality onto the aromatic portion of the PPT molecules. Introduction of an epoxy functionality has also been attempted (25, 26). Hydrolysis of the PPT surface was used to introduce the functional group for epoxidation but the degree of the hydrolysis was found to strongly influence the mechanical strength of the fibers (25).

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Very recently, the surface treatment studies of ultra-high modulus polyethylene fibers has been reported. Chemical treatment by chromic acid (27, 28) or fuming nitric acid(29), corona discharge(30) and plasma treatment(31) are some of the techniques used. In many cases, the effectiveness of the surface treatment was reported to decrease as a function of time, probably due to the molecular mobility of the surface species. 5.6. Selection of Materials Selection of materials is based on the preference in properties that need to be achieved. Let us suppose that one desires a composite with very high tensile strength. The first choice is very high strength fibers such as carbon fibers, S-glass fibers, poly(para terephthalamide) or ultra-high modulus polyethylene fibers. Then, a resin is chosen so that the compatibility and processibility is appropriate with the fiber chosen. If further properties are desired, for example, hydrothermal stability, then more severe selection will be imposed on the resin, the reinforcing fiber, and the surface treatment method. Since composites are heterogeneous, the selection of materials only is not sufficient. One must also consider the form or topology of the reinforcement. Would it be fibrous or powdery? Or, would it be woven cloth or simple roving ? Once the proper materials and their forms are selected and the compatibility is adjusted by a surface treatment, the materials are subjected to processing. 5.7. Selection of Processing Methods No processing machine or method is universal and, therefore, a proper selection of a processing method must be made for each reinforcement/resin system. When one selects a processing method, the following factors play a major role. A. Aspect Ratio of the Reinforcing Material This is the length/diameter ratio of the reinforcing material. Usually, a reinforcing material with a high aspect ratio is difficult to injection mold or extrude, thus a particulate-filled, milled glass fiber-filled or chopped glass strand-filled resin is used for this type of process. Continuous fibers are used for filament winding and pultrusion. Sometimes, preforms made of continuous fibers are used with reaction injection molding and resin transfer molding. Woven materials are suitable for compression molding, hand lay-up processing, and pultrusion. B. Shape of the Final Product Screw injection molding can make complicated shapes while compression molded parts are relatively simple. Intermediate complexity can be achieved using transfer molding or plungertype injection molding. Filament winding can produce relatively complex shape with dull curvatures while pultrusion produce complex shape only in the cross-sectional direction. Among the pultrusion method, vertical pultrusion is suitable for more complex shapes than horizontal pultrusion. However, the majority of pultrusion is now done using horizontal pultrusion. Hand lay-up and spray-up methods are time and labor consuming but can be used to produce large, complicated shapes. C. The Time Necessary to Form Hard Solid This concept applies mainly for thermosetting resins since most of them are either liquid or soft solid. Thermosetting resins require chemical reactions during processing in order to form usable, solidified composites while thermoplastics need only to experience a solidmolten liquid-solid cycle without chemical reaction. Using thermal polymerization, chemical reaction is relatively slow and requires somewhat a long hold-up time of the machine per part. 14

Filament winding is usually used for high performance composites and the time consideration is more relaxed. Pultrusion, on the other hand, is a continuously flowing system and curing time is very short on the order of a few minutes. Compression and injection molding generally require 2 to 20 min for thermosetting matrices while the autoclave method utilizes longer times. Stamping is a form of compression molding but it utilizes a preheated resin and the time necessary to complete a part is much shorter than regular compression molding. There are other factors to be considered such as the viscosity or the reinforcing material/resin mixture, the effect of shear rate on the interfacial bonding, degradation of resin and reinforcing material by the shear stress and the heat generated by both the shear, etc. However, each method is unique in its own right and different processing methods are seldom interchanged for the above reasons. 5.8. References 1. 2. 3. 4. 5. 6. 7. 8. 9. E.P. Plueddemann in "Molecular Characterization of Composite Interfaces", H. Ishida and G. Kumar, Eds., Plenum, New York (1985) p.13. "Interfaces in Polymer Matrix Composites", E.P. Plueddemann, Ed., Academic, New York (1976). "Silylated Surfaces", D.E. Leyden and W. Collins, Gordon and Breach, New York (1980). E.P. Plueddemann, "Silane Coupling Agents", Plenum, New York (1982). "Molecular Characterization of Composite Interfaces", H. Ishida and G. Kumar, Eds., Plenum, New York (1985). H. Ishida and J.L. Koenig, Polym. Eng. Sci., 18, 128 (1878). H. Ishida, Polym. Composites, 5, 101 (1984). H. Ishida and J.L. Koenig, J. Polym. Sci. -Phys., 17, 1807 (1979). H. Ishida and J.L. Koenig, J. Colloid Interface Sci., 64, 555 (1978).

10. S. Naviroj, J.L. Koenig and H. Ishida in "Progress in Science and Engineering of Composites", T. Hayashi, K. Kawata and S. Umekawa, Eds., ICCM-IV, Tokyo (1982) p.227. 11. J.D. Miller and H. Ishida in "Silanes, Surfaces, and Interfaces," D.E. Leyden, Ed., Gordon and Breach, New York (1986) p.525. 12. H. Ishida, J.L. Koenig and K.H. Gardner, J. Chem. Phys., 77, 5748 (1982). 13. C.D. Han, C. Sanford and H.J. Yoo, Polym. Eng. Sci., 18, 849 (1978). 14. J.D. Miller, H. Ishida and F.H.J. Maurer, (submitted). 15. H. Ishida and J.L. Koenig, J. Polym. Sci. -Phys., 17, 615 (1979). 16. E.P. Plueddemann,"Silane Coupling Agents", Plenum, New York (1982) p.134.

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17. H. Ishida and J.L. Koenig, J. Polym. Sci. -Phys., 18, 1931 (1980). 18. J.V. Hallum and H.V. Drushel, J. Phys. Chem., 62, 110 (1958). 19. H.P. Boehm, Angew. Chem., 6, 533 (1966). 20. J.B. Donnet, Carbon, 6, 161 (1968). 21. A. Ishitani in "Molecular Characterization of Composite Interfaces," H. Ishida and G. Kumar, Eds., Plenum, New YOrk (1985) p.321. 22. J. Delmonte,"Technology of Carbon and Graphite Fiber Composites", Van Nostrand Reinhold, New York (1981). 23. L.T. Drzal, M.J. Rich and M.F. Koenig, Proc. 38th Ann. Tech. Conf., Reinforced Plastics/Composites Inst., SPI, Section 4-F (1983). 24. R.E. Allred, E.W. Merrill and D.K. Roylance in "Molecular Characterization of Composite Interfaces," H. Ishida and G. Kumar, Eds., Plenum, New York (1985) p. 333. 25. T.S. Keller, A.S.Hoffman, B.D. Ratner and B.J. McElroy in "Physicochemical Aspects of Polymer Surfaces," K.L. Mittal, Ed., Plenum, New York (1983) p.861. 26. H. Chatzi, H. Ishida and J.L. Koenig in "Composite Interfaces," H. Ishida and J.L. Koenig, Eds., Elsevier Science, New York (1986) p. 285. 27. 28. 29. 30. 31. I.M. Ward and N.H. Ladizesky, Pure and Appl. Chem., 57, 1641 (1985). I. Ward and N.H. Ladizesky in "Composite Interfaces," H. Ishida and J.L. Koenig, Eds., Elsevier Science, New York (1986) p.37. A. Taboudoucht and H. Ishida, Polym. Composites (submitted). S.L. Kaplan, P.W. Rose, H.X. Nguyen and H.W. Chang, SAMPE Quaterly, 55 (1988). N.H. Ladizesky and I.M. Ward, J. Mat. Sci., 18, 533 (1983).

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