46th Anal Conlemnce, Compose hati, The Society of he Posts neat, nc february 18-2, 1991 B. Tomas AsTROM* R. BYRON PIPES** Modeling of a Thermoplastic Pultrusion Process ABSTRACT ‘To obtain a fundamental understanding ofthe ess of processing pa rameters and die geometry in a pulruson process, a mathematical model ‘sesential in onder to minimize he mmber of trial and error experiment, Previous workers have svgesieda varity of more or less complete models for thermoset pllrusion, while ite effort sems to have been spent mod ‘lng it less well understood thermoplastic eqvalet Hence seo nuicatly relied modesto describe the temperature and pressure dstbutons, aswell asthe mats fow, in a thermoplastic com- ost ast travels trough the plirusion die, i presented. Am approach 0 culate the accumulated paling force is also explored, and the individual ‘mechanisms contributing 1 he paling force are discussed. The pressure ‘model incorporates a matrix vicosiy that varie with shear ate, pert {re and prestue, Comparions ae made between shearrae-dependeat and Newtonian viscosity representations, indicating. the necessity of including non-Newtonian betavor when modeling thermoplastic plta- sion, The goveraing equations of the models are stated in general ters and ‘arious simplifeaions are implemented in onder 1 -cbain solutions ‘without extensive numerical eons, Pressure, temperature, cooling rate and puling force distutions are preseated for polyether etherietone Pilling force predictions are compared to data obitined from preliminary ‘experiments conducted witha model pultusion line that was bult solely forthe pllrusion of thermoplastic marix composites, andthe corelation is found tobe qualitatively satstacory. INTRODUCTION variety of models aimed at gaining a thorough understanding a thermoset pultrusion process has been suggested in the ‘ast. While all ofthese have treated only part ofthe problem, such 8 heat transfer and cure kinetics or pressure and flow relations, the ‘work of Batch {I atempis to address all the phenomena. His anal _yses of composite temperature throughout the die compare we, With experimental results, while his comparisons between predic- tions and experiments for resin pressure and pulling force are in- ‘conclusive, While considerable effort has been spent analyzing and model- ing a thermoset pultrusion process, 10 the knowledge of the author, very litle has been spent considering the special problems ‘of its thermoplastic equivalent [2]. Hence, a project aimed at gain- ing a complete understanding ofa thermoplastic pultrusion process ‘was initiated. On the one hand, detailed theoretical analyses ofthe process were conducted, while, on the other hand, an experimental “Deparment of Aeronautical Sivcures ond Mateos, The Royal I~ sfiuie of Technology, 5-00 44 Stoctholm, Sweden. **Center for Composite Moterols, Unversity of Deloware, Newark, DE T9716, USA poltrusion line was builtin order to verify the analyses and to ad- Gress practical processing problems. This paper presents the [governing equations of the theoretical analyses as Well as their Solution for simplified conditions. The limited, experimentally ob- tained pulling forces correlate qualitatively well with the predicted ‘ones, providing initial confirmation of the basic soundness of the theoretical analyses. GOVERNING EQUATIONS Since a pultrusion die for thermoplastic matrix composites most likely would have a significant entrance taper where resin flow ‘would occur, we will for the initial pressure/flow analyses concen- ‘rate our efforts on a two-dimensional taper (Figure 1), We assume that the process is at steady state, that the fibers in the over- saturated bundle entering the die are parallel to the pulling direc- tion, and that all resin flow is parallel to the fibers. Fiber Continuity Equation ‘The fiber continuity requirement emanates from the assumptions ‘that all fibers are infinitely long and that their number is constant. ‘This reasoning will, however, give us no information about the dis ‘ribution of fibers inthe z-direction. This distribution would be ex pected tobe statistically varied, asthe integrity of tows or rovings ‘Would be maintained throughout most, if not all, of the manufic- turing process and the relative fiber locations would vary with time, For lack of beter alternatives, we will therefore assume that the fiber distribution is transversely isotropic; i, it does not vary ‘with the z-coordinate, The continuity equation forthe fiber volume fraction along the x-axis may be written as @ where v(x) is the fiber volume fraction, h(x) half the height ofthe die, vg = (Dy hz = WL), and x = Lthe length of the taper (see Figure ). In the case ofa linear taper, we may write this as @ where t= ¥(0) Session AT |Resin Continuity Equation ‘The resin continuity equation may be obtained by considering the resin flux through two diferent control surfaces (in the y-2 plane) in the taper: one at an arbitrary coordinate x and one at = L._ Atthe former the resin Mux isan unknown, and athe later the resin travels atthe same velocity asthe fers. We writ the resin flux through the two contol surfaces as ght) = UU = vdhe © where q isthe flow rate per unit area and U the constant pulling Speed. Using Equation (D, the expression fr the resin Now rate becomes 1- = toy o ‘One could, of course, also introduce Equation (2) into this ex- pression to get the flow rate in terms of te x-coordinate rather than the fiber volume fraction. However, for reasons of convenience, we will use the fiber volume fraction as the independent variable throughout most of this treatment. Flow Bq ‘The relation used to model flow through aligned fiber beds has traditionally been Darcy’s law with the Kozeny-Carman expression for the bed permeability introduced (3). Whereas these expres- sions adequately describe the flow of Newonian fuids through beds of spheres, the form of the Kozeny-Carman expression ‘modified for flow tough beds of aligned fibers has proved cons erably less accurate. Using the modified form of the Kozeny- Carman expression, the resin pressure drop, AP,, of a Newtonian fluid over an aligned fiber bed of thickness L, may be weitten as (3) ap, King L q a=¥P where K; isa shape factor depending upon the shape of the cross- section of the supposed capillaries of the porous medium; K, isthe tortuosity, defined as the ratio of the distance traveled by a fuid clement and the thickness/length of the medium; 7 isthe resin vis- cosity; and r; isthe fiber radius. The fiber volume fraction v(x) hhas here been abbreviated. The Kozeny-Carman approach assumes that the group KK, usually referred to as the Kozeny Constant, is independent of flow direction, fiber volume fraction, fluid, fiber, and pressure gradient. However, data from exper ‘ments with real fiber beds show tha the Kozeny constant depends ‘on al ofthe above and also that there is considerable scatter in the experimental results [3]. However, tothe knowledge ofthe authors there is currently no realistic alternative to using said expression 0 relate a pressure drop over a fiber bed to the flow rate through it Due to the uncertainties in determining the value of the Kozeny constant, pressures obtained by using the Kozeny-Carman expres sion forthe permeability will always be uncertain, but the analysis, should sil be qualitatively correct so that parametric studies are valid ‘Equation (5), which was derived for Newtonian fluids, can not bbe expected to accurately describe the flow of thermoplastic melts, as these show considerable shear thinning tendencies. In our previ ‘ous work we showed how the shear-thinning effects of a uid may bbe accounted for using the power-law and the Carreau models, and it was pointed out that, at least for the pultrusion process, the latter is preferable (3). The apparent viscosity of the Carreau model may, for a polymer melt, be writen as ne = nell + GI © o 2/ Session 4-8 where 1p isthe zero shear-rate viscosity and 4 the shear rate. The time constant, A, indicates the shear rate at which shear-thinning ceflecs become important, and the dimensionless constant N describes the degree of shear thinning. Using this viscosity repre- sentation, one may obtain (3} aR _AKKing 2kidg__\ cal (aa) Jo which isthe Carreau madelequivalest of Dare’ law. I is easily Seen that if V = 0, corresponding toa Newtonian fi (see Equa: tion (6, Equation (P) reduces to Equation (3), which also isthe case at very low flow rates (and, hence, shear rates), when polymer melt exhibits Newtonian properties. This equation is, ax Sf yet, unverified for fiber beds, whle is equivalent for sphere beds as been shown to corelate weil with experiments. with polymer melts [4 It must be understood that Equation (7) is sub- ject at eat, the same restrictions as Equation (5), sothe deter Imination of appropiate values for Ke and Kis adificult endeavor As discused above, itis nevertheless argued that by assuming these parameters trve constans, we do not disrupt the qualitative resuls of our analyses. Resin Viscosity ‘The viscosity used in Equation (5) and the apparent viscosity T.), and then the steond die, which is cooled (7 < T,). Both between the dies and after the second die, the composite is cooled by convection, The ‘numerical parameters used in the examples below are shown in Table | Pressure Only a generic die taper vas treated in the above pressure /Nlow analysis. It is herein assumed that the resin pressure created by the back flow in the taper ofthe heated die wll be maintained through- ‘out the uniform cross section portion of the same die. If the tem- perature ofthe resin increases inthe die, the resin pressure will be ‘increased by the thermal expansion due tothe assumption thatthe ‘composite travels through the constant cross section part of the die ‘as a solid, This will crete a monotonically increasing total resin, pressure, which, at @ poi near the end of the die, will very ‘quickly decrease to ambient pressure. Inthe present analyses, this resin pressure decrease is assured to cur instantaneously at the fend ofthe die, s ts nature is unclear and its infuence on the pull- ing force calculations is assumed to be small. In the pressure ex- amples we will assume thatthe preheater raises the temperature of the impregnated fiber buadle to a temperature equal to that of the dic, which allows thermal expansion effects in the heated die to be paction and the temperature induced fares, Factors considered in cluded resin viscosity, die emperature, material thermal expan- sion, Tine speed, and die geometry factors. Major conclusions concerning the bulk compaction componeat of force were that a linear increase in fiber volume had an exponen: tial influence on pulling force and that the greater the affected length (and width) along the die of a fiber volume change the eater the influence on pulling force. Insights relative to the tery- Peratute induced forces include the abservation thatthe pulling speed which produced the best quality (as measured by specific _gravity and short beam shear strength) was that which also exhib ited the maximum pulling forces This observation recognized the need to maintain the reaction within the die despite the higher pull ing forces which occur due to thermal expansion and gel adhesive debonding. Despite the acknowledged limitations of the experimental ap- proach this work gives us the frst foundation fora model which at- {empts to predict the pulling forces from characteristics ofthe die, ‘materials, and process parameters. Bibbo (1986) attemprs 1 refine the equations for frictional forces, viscous forces, and resin back flow forces but bases the derivation on a rectangular dic with con- stantly contracting (tapered) length [3]. He reports that at low resin volume fractions, the pulling force is more dependent upon the frictional force component than the viscous drag or back fla com ponents of total force. The linea Trictonal force equation is based‘upon fiber volume and uses a Fiber Deformation Model which considers the forces required to compact impregnated fiber bundles having imperfect fiber alignment. The change in predicted force with increasing fiber compaction ratio is discussed. The pull- ing force data of Price is then examined for fit othe model. Since the die utilized by Price is not tapered over its length and has only small encance radius, the resin backflow prediction is of limited felevance. The viscous drag equation predictions do not match the data presented, however, the frictional force predictions were found to closely agree with the data reported by Price for diferent fiber loadings of prepregged tape. ‘The roe ofthe elidie interface in terms of adhesive shear forces is discussed by Outwater in 1987 in qualitative terms [4]. The recognition of this contribution to friction along. with those of Potential die-fovling mechanisms referred to as “pling” (powder- Ing of adhered resin) and “collaring” (constriction of the die area by an adhered resin sheath) are discussed in this work. The impor- tance of internal mold release to reduce adhesive shear strength (promoting die debonding) is also postulated along with limited data showing that too much internal release has a deleterious effect ‘on composite properties, The significance ofthis concept is ver fied in later work by Bryan etal (1989) wherein the type of internal ‘mold release used is shown to have a major efect on the overall pull load measured. With six commercial releases evaluated, 2 ange 240 to 450 Ibs. of pull force was observed at equal mold release concentrations. They further observed that after selection of “good” mold release, pul force is relatively insensitive to mold release level although 90 data is offered below .S phr where adhe- sive debonding stress i likely to increase sharply Batch (1987) is the fist to present a complete numerical model \hich offers relationships for heat transfer, resin curing reaction, and pulling force in a pultrusion di. The heat transfer model is simplified by selecting round geometry, negating any influence of, pressure on reaction rate, and ignoring thermal expansion of the fibers. In addition o these assumptions, the resin pressure model assumes tha the fibers act as an anisotropic porous media and that there is no transverse dependence of fiber volume fraction on pressure. With these assumptions a pulling force model is pro- posed for @ round die which considers the bulk force, viscous fore, and friction force components utilizing terms for line speed, fiber elastic stress, and friction coefficient ofthe gains the die wall. The novelty ofthis approach isin the coupling of reaction kinetic predictions of the location of ‘onset of gelation and die separation to quantify the lengths of the Viscous drag and gelation repions. The assumption of zero friction after the gelation zone also limits the pull force predictions o cases ‘where net shrinkage due to cure exceeds thermal expansions which is ot always the ease as we will discuss ata later ime. The author acknowledges the ned for further development of quantitative data for friction coefficients for the resin with respect to the die at various temperatures, degrees of comersion (gel state), and line speeds before useful predictions can be offered. ‘The remaining papers cited in the bibliography have to do with ‘experimental studies in full scale putrusion processes which ex plore the empirical relationships of the numerous variables found in pultrusion. Sumerak (1985) presents a method of studying inter- nal die pressures and external pulling force in all unidirectional re inforeed rectangular profile tilzing flush diaphragm transducers in the die and an external load cell respectively [2]. The ex- perimental program evaluated effects of filler content, line speed, and volumetric shrinkage onthe position and magnitude of internal pressures and their influence on external pull resistance. The Strong dependence of pull load on line speed is coupled with mea- surements ofthe postion of peak exotherm temperature (a measure ‘of material reaction) and the magnitude of the intemal pressure profile measured. The magnitudes ofthe internal pressures were found tobe substantial (above 100 PSD and dependent upon initial resin viscosity, filer content, line speed and resin volumetric shrinkage. Internal pressure profiles for both uncatalyzed and catalyzed resins were studied 10 de-couple viscous drag from reac- tion induced gel friction. The decay of internal pressure as a func: tion of time after a line stoppage was also examined. A major con- tribution of this study was the discussion of the qualitative ‘mechanisms ofthe inter-related dynamic aspects of materials and ‘cure reaction within the die, The strong direct relationship of pull force to line speed, to filler content (or total solids content) and to net volumetric shrinkage is verified. The evidence of a non-zer0 friction component after the gel zone associated with lo shrink resin ystems isa behavior not addressed in previous models, ‘The work conducted by Sumerak employed isophthalic polyester resins, Three papers were presented in 1988 and 1989 regarding pull force measurements with three alternative resin systems Howard et al. (1988) reported on the factors affecting pall force for thermosetting methacrylate resins (6). With a force transducer coupled to the die, a 160 inch X 3 inch flat strip was pultruded ‘with unidirectional fibers and a methacrylate resin which had been filled with various particle size fillers in the 8 w M4 micron range. ‘They found that pull force cannot be predicted from viscosity alone ‘but rather that particle size of filler was the most significant factor at any given glass loading. The larger the filler particles the higher the pull loads and the ower the maximam achievable fiber volume. Below a cerain minimum filer and glass loading poor surface condition and pull load instability resulted requiring frequent die purges (self-cleaning stop-start sequences). A high pull force was ‘required to obtain best quality parts and this could be achieved by ‘combination of line speed increases and fiberfiller ratios. The largest particle size fillers actualy limited the maximum line speed achievable based on exceeding the pulling capacity oftheir pultu- sion machine. Hunter (1988) describes the unique characteristics of epoxy resins for pultrusion [7]. One of the best descriptions of internal dynamics is presented herein with special emphasis devoted to vis- ‘cous shear forces, gel cohesive forces, and sliding frietion in the release zone. The special Sensitivity ofthese resins to fiber loading is described and the need to provide sufficient internal pressure 10 prevent sloughing (resin build-up) in the die. An optimum pull, otce plateau is identified as isthe sensitivity of pull load to contol temperature locations in single zone and two zone heating systems, ‘Annovel comparison ofthe differences in volumetric shrinkage rate land curves of polyester and epoxy resin is presented t clarify the ‘unique processing requirements of the pultruded epoxies. Bryan etal, conducted experiments on vinyl ester resins with a roving reinforced II inch by 1. inch lat strip [8]. After screening for optimum mold release as previously described, designed ex periments were conducted to explore the sensitivity of pull force 10 the mixture proportions of resin, glass, and filer. Response sur- face plots are generated using trilinear ploting for three different, line speeds. Their findings provide a new perspective on the im- portance ofthe relative ratios of composite components by suggest- ing thatthe resin volume fraction is of primary importance due to its lubrication and volumetric shrinkage attributes Further investigation of resin debond shear stress is conducted bby Lamb et al. (1989) for a .200 inch diameter round rod. A low profile polyester resin is used for these studies which follow a {inch long plug of impregnated roving through a die while recording. pull load changes. Three zones of pull force peaks are identified associated with viscous drag, resin debond, and Coulomb friction, ‘of the cured plug against the die wall. The effect of line speed on ‘the magnitude ofthese peaks is observed. The observation of con- tinued friction after debond is reported and can be attributed to the low shrink characteristic ofthe resin EXPANDING THE SCOPE ‘The studies summarized all provide valuable insights into the ‘mechanisms of internal friction development and the factors afect- Session 4-B/2ing pull force. A review ofthe profiles geometries, resins, and die lengths used by investigators is shown in Table I I'can be seen that as is the tendency with numerical model development, investiga- tors tended to simplify their studies by choosing simple profile geometries which provide unobstructed shrinkage away from the die wall. Figure I(A) illustrates this freedom of movement which results in lowest possible frition after debonding. The majority of commercial products are non-uniform cross-sectional. profiles Which shrink in both directions, perpendicular and parallel to the thickness of the section. Figure i(B) shows that fora C-channel the transverse. shrinkage of the horizontal web can result in 2 ‘mechanical friction against the two interior vertical surfaces of the die (highlighted surfaces), With unrestrained shrinkage in the transverse direction of the vertical flanges, there is no drag on the bottom of the horizontal web. However, by adding a small inward return tothe C-channel, shrinkage becomes restrained in both hor- ‘zontal and vertical directions causing an increase in friction. Ad- tional cases where profile desiga can affect mechanical drag fric- tio are shown in Figure (C), KD), and 1(E). In each ease the profile will shrink onto the male section and away from the female cavity. The friction for the profile Figure I(E) arises from the shrinkage onto the mandrel and the lateral movement of the side Wings towards the center. Die design can be modified to reduce shrinkage by providing a release taper such thatthe die dimension is reduced on selected surfaces of the male section. This action when done properly can reduce internal stresses in the profile which leads to better surface appearance and improved control ‘over linear dimensional tolerances such as bow and twist. While fairly easy to implement on fat surfaces, it is more dificult to im- plement on curved surfaces such as are found in the profile of Figure I(E). A negative consequence ofthis die design approach is, the elimination of the option to run the die from either direction since it is not possible to pultrude through a gradually constricting ceavity (from larger exit toward smaller entrance) ‘Another examiation of prior experimental programs will show thatthe only reinforcement used was unidirectional roving which provides the best volumetric packing and easiest resin back flow Conditions. Models proposed to date also limit their scope to this ‘common reinforcement: Commercial products other than rods are [generally composed of a combination of random fiber continuous ‘Strand mats and unidirectional rovings but also may include biaxial fabrics and surface veils. These reinforcements present much dif- ferent surface drag behavior, fiber bulking characteristics, and resin back flow conditions all of which have been identified as im- portant factors in internal frition development. In addition, these ply materials have limited or zero fiber mobility which is an im- portant favorable characteristic ofa unidirectional roving compos- ite, AS a result, local stresses from high fiber concentrations in a ‘mat or fabric cannot be distributed by transverse fiber motion within the ply ‘The typical orientation issues which give rise to local stress or friction variations are shown in Figure 2, The profile of Figure 1G) is shown in more detail in Figure 2 as it represents a mode aly complex profile with multiple plies of continuous strand mat ‘ith unidirectional roving sandwiched between mat plies. Figure 2 shows the mat ply orientation which provides complete wrap of the hollow section and continuous surface coverage ofthe perimeter of. the shape. There are several possible sources of local density varia- tion shown inthis figure. Figure 2(A) shows a high density condi- tioa that can occur atthe termination of a profile appendage where the overall width of the mat might be excessive. The mat must fold ‘or bunch in this area to enter the die causing a high glass content along the entire length of the die in this area. It is particularly a problem in a tapered edge as with this profil since exact placement ‘of mat is difficult. Conversely if a mat isnot wide enough this ex- ‘reme termination point will be low in density and insuficient packing may result in resin sloughing or loss of dimension, Loca- tion 2(B) points out a local high density area resulting from a mat 3/ Session 4-B ply overlap which is necessary to oblain the best structural strength. Location 2(C) shows an area of potential low density due to increased cross section atthe intersection of profile elements Such an area usually displays mat folding problems as a result of Tree material movement under pressure in the fluid zone or as a result of poor forming control. Such an area is going to be prone to resin sloughing which may result in pull force instability as chips of adhered resin ae periodically forced out of the die due to pressure buildup. This can be solved through improved materia placemeat and temporarily treated with programmed purge eyles, ‘Which clean out te die. Location 2(D) represents a local pressure point caused by a roving knot, a hard roving spice, or even a local high density mat area. ‘The severity ofthe effect of local stresses can range from min ‘mal detectable load variation to catastrophe. If there is sufficient mobility of adjacent fibers to relocate around the inclusion, litle effect will be registered. If the inclusion is such that an extreme local pressure causes tearing of fibes, the tear can progress into a highly packed region behind the defect and a total breakout of ‘material may occur with a rapid increase in pul force. Often this, can occur So quickly that a breakout cannot be averted. However, if'a high pull-load alarm feature can cause the machine to pause early enough, the obstruction may be able to be cleared before complete disaster occurs, ‘THE PULSE OF PULTRUSION ‘As can be seen from the background work and the previous dis- ‘cussion, there are a lot of factors that are universal in their n+ fluence on pull force such as the line speed, fiber content, filler ‘content, mold release concentration, and reaction rate. There are ‘other factors that are specific tothe type of resin used, the volummet- rc shrinkage rate, the type of reinforcement, the effectiveness of forming, the geometry ofthe profile, and the occurrence and type ontribute to the level and stability ofthe external take @ very complex model to address all ofthese issues for other than the simplest shapes. It can be seen clearly that the magnitude of the pull force will vary from profile to profile with diferent material compositions. An optimum balance of fac~ tors will result in pall load subility with only moderate variations ‘due to the randomness of fiber alignment and ply weight distribu tions "To use a physical analogy, there is @ normal blood pressure and pulse rate that a healthy individual exhibits. A change in blood pressure or pulse rate throughout the day reflects a normal re sponse to level of activity and will not cause a problem. Too high 2 stress level or physical exertion will result i an increase in pulse rate. A constriction in the flow of blood through the veins can ‘cause an increase in blood pressure. An extreme high blood pressure condition can result in severe physical damage and even ‘death. Too low a blood pressure can also be a serious problem. An individual in physical jeopardy must have his vial signs monitored ‘continuously for stability ‘Without belaboring this analogy, the pull force in pultrusion can be considered the pulse rate of the process und a measure of its health. Too low a pull force results in instability and poor quality ‘An obstruction inthe movement ofthe material through the die can ‘cause an increase in pull force and too high a pull force can lead to catastrophe (breakout) if corrective action is not undertaken. A ‘continuous monitor ofthe pull force can be an extremely valuable tool in sustaining quality production of commercial proiles. ‘THE CHALLENGE OF PULL FORCE MEASUREMENT From 2 fundamental standpoint the best place of measurement is inthe die where the individual components of pul force can be iso lated. It is here thatthe most information as othe source of indi- Vidual contributions is availabe. To date the only continuous mea-surement of internal pressures has been found in the work by Sumerak [2]. Thee points of internal pressure were measured us- ing lush diaphragm transducers as part ofthe die wall. The tec nique was successfl in defining an internal pressure profile which ‘did move in response tothe variables previously discussed and pro vided a significant new insight. From a practical standpoint, bow- ‘ever, there are several limitations to this approach. The firs isthe Giscontiouity of data when only a few points are instrumented along the die length requiring the interpolation of data between ‘measurement points. Based on subsequent studies, non-linear be havior between measurement poins is very probable and impor lant peaks or tendencies may go unseen. This could be resolved ‘with multiple transducers with close spacing; however, the expense, and practicality of this approach is imitation, The diaphragms of sueh transducers are very thin and fragile and are easly damaged by abrasive wear and resin adhesion (especially with epoxies). The flat diaphragm surfaces and the dimensional tolerance of the dis- ‘phragm depth relative to te die walls critical in obtaining mean- ingful results. Inthe region in which the product releases from the die wall, pressure cannot be detected even ifthe product is pressing, ‘against the wall due to the smal local deformation of cured ma- terial as it passes over the tcansducer face. A full scale load is, typically measured at 003 to 004 inches of deflection of the di- phragm, These limitations preclude the use of this technique in production ies ‘An alternative to continuous internal pressure measurements is described in a paper by Fanueci etal. where a thin flat sensor called a force sensing resistor (FSR) can be inserted inside the material entering the die. This thin sensor (O12 inch thick, {625 X 78S inch rectangular) changes is resistance with applied force and can track the development of forces throughout its resi ‘dence time in the die. This technique is suitable for research and engineering studies and is considerably less expensive than fixed transducers, but it also has @ numberof inherent limitations. The first limitation i thatthe data represents a point in time and as we have discussed the friction conditions can change rapidly in the die ‘requiring multiple tests to gather desired data as process conditions change. A bigger limitation arises from the form of the sensor itself Ina die cavity of 120 inches in thickness, introducing ¢ 012, thick sensor of 625 inches width will increase the relative fiber volume in the sensor footprint area by 11% sinoe the available area for fiber is reduced. This will result in an artificially high force from fiber compaction. This is mitigated to some degree if there is, fiber mobility for example in a roving phase that can reduce the local fiber volume. This is not a possibility in an all fabric compos- fe and likely higher load will be egistered than is experienced in areas adjacent to the sensors. Sensor to sensor repeatability is advertised as + 15% although special compensation can be made. In sum, despite the simplicity of the test procedure and its low cost, i is best for relative comparisons. “Another similar intermittent tet method but different technology is that offered by Metricore where the seasor is 2 006 inch di meter fiberoptic device which converts the change in light trans: mission caused by fer compressive stress to a force valve [I]. ‘The instrumentation necessary with this approach provides signal amplification, linearization, and temperature compensation. AS is shown in Figure 3, the effect on local fiber volume ofthis sensor type is insignificant compared to that of an FSR especially in @ ‘mobile roving phase. The technique, however, is more sensitive to ‘mishandling or kinking ofthe fiber in the guiding system. The cost per test ofthis approach is high and ths limits the applicability to R&D studies. ‘Since existing internal pressure measurement technology cannot bbe easly applied othe production environment the next best alter- native i external measurement ofthe net pulling force required to ‘overcome the internal resistance caused by the multitude of factors described. The best approach, and that utilized by all of the ce~ ‘searches cited, isto couple the pultrusion die directly to a force transducer which can measure in ether a tension oF compression ‘orientation, the restraint of the die as the product is being pulled Ifa transducer isin direct contact with the die a temperature com- pensation feature must be selected from the supplier. This direct approach is difficult to apply to multiple cavity processing and pre~ cautions must be taken to preclude handling damage and mecha ial shock damage ofthe transducer. 'A second best approach isto detect the same restraining forces fon a die mounting tale or frame that is designed to provide low friction linear motion to transfer load to the transducer. Multiple die tables ean be used or a signal transducer on one table which holds multiple dies. In either approach power supply, signal amplification, filtering, and linearization instruments are neces- sary and available to obtain a meaningful readout, Calibration of such instruments directly in pounds (or kilograms) is desirable ‘The most common production method of sensing pull load is to monitor a characteristic of the pulling device itself. There are ‘many different puller designs and power sources in the industry. Belted or caterpillar cleated-chain pullers provide a continuous palling motion and can be driven by either AC or DC electric motors or hydraulic motors through a mechunical transmission Current or power for electric motor drives and hydraulic pressure for hydraulic motor drives are suitable signals which can be di played directly in current, power, or pressure units. To obtain dis- ‘lays in pounds of linear thrust itis necessary 10 have knowledge fof the mechanical transmission torques, reductions, and motor ‘characteristic curves which makes this conversion a bit difficult, ‘A second very popular machine design utilizes a reciprocating clamp puller where two carriages alternately grip and pull the product in order to impart a continuous pulling motion. Mechan- al and hydraulic versions ofthis machine type are available and again electric motor current or hydraulic pressure sensing are Suitable approaches. ‘The alternating pulling action of such machines, while providing a number of advantages tothe proces- sor, does make pull load sensing a bit more complicated as load is. transferred from one carriage to another. This load signal transfer function can be accomplished with either electronic relays or Inydraulic valves but itis ike that a load display meter will show brief load signal peak or tough associated with this action which is not seen on the continuous drive machines. ‘Any ofthe machine load sensing approaches are measuring both the resistance ofthe product being pulled and the power required to eyele the machine itself. For this reason, for an absolute valve of pull load rather than a relative value iti desirable to establish, ‘a machine baseline calibration curve which can be used to adjust the pall Toad signal “The advantage of such machine signal sensing methods is that they are generally more durable and less costly to apply than die sensing approaches and can be integrated easily to other functions ‘of machine control. A disadvantage arises in multiple cavity pro- ‘esses where the machine cannot distinguish between the load re ‘quired on an individual die basis but instead measures the entire Pull Toad of all cavities. DISPLAYING PULL FORCES ‘The display of pull force can take many forms. The display of a machine parameter such as current or hydraulic pressure on an analog meter or mechanical dial giuge can give a reasonable felative indication of load as long as fll scale capacity is known ‘With the popularity and low cost of digital process meters this same information can be displayed in digital format with internal cali bration for any engineering uit, e.g., amps, PSI, KW, or percent, although a more meaningful display would be pounds or kilograms Of force and can be arrived at through transmission calculations, A Pro. 50h SAMPE BIOGRAPHIES. Joseph E. Sumerak Joseph E, Sumerak received a B.S. Engineering Degree in 1973 from Case Western University Department of Macromolecular Science. He has worked in industry in research and development, ‘and manufacturing engineering roles and has had experience in ‘thermoplastic, eubber, and thermoset processes. The past fifteen years of experience have been primarily devoted 10 the advance ‘ment of pultrusion process technology initially with the laste ‘Company and since 1981 with Pultusion Technology which he co- founded with Jef Martin. Since tis time he has been responsible for the development of machinery toting, and process techniques for Pultrsion Technology which has specialized in puliusion equipment productivity through process control. Mr. Sumerak has ‘authored and co-authored numerous technical papers on the tech- ‘nology of pulrusion and has been a member of industry organiza tions such as SPE, SME, and ASTM. In 1989 Pultrusion Technol ‘ogy was aequited by MMFG and Me. Sumerak currently holds the position of Technical Director. Jeff Martin Jeff Martin is Managing Director of Pultrusion Technology, & Division of MMFG. PTT is the world’s leading manufacturer of production-oriented pultrusion machines. PTI focuses exclusively, ‘onthe pulirusion process coordinating the thre critical pultrusion areas of equipment, tooling and product/compesite technology. ‘Mr. Martin is a 1967 graduate of Penn State University with a BS. Degree in Business Administration. Martin has nearly 24 years of experience in sales, marketing management and product ‘anagement involving all aspects ofthe pultrusion process. He has had nine years of experience with Owens Corning Fiberglas in the ‘aw matfial side ofthe process, five years experience in marketing pultruded profiles, and the lat ten years in the pultrusion equip- ‘ment market with Pultrsion Technology. Jeff Martin has been active in many technical publications of pultrasion and has given many seminars on the subject, For the last, {en years, Mr, Martin has acted as Coordinator for Pultrasion Ses- sions at the Reinforced Plastics/Composites Institute (Society of the Plastics Industry) Annual Conference. A member of ASTM. 'D2002 on Pultruded Shapes, Martin authored a chapter on pultru- sion for the Handbook of Plastics Products Design published by ‘Marcel Dekker, Inc. in 1983. He has been chairman of the SPI's, Pultrasion Industry Council and is a member of SPIs Composite Institute Board of Directors, Session 4-816TABLE 1. Summary of Experimentel Approaches ‘stile. tachan tha Uaneths Inches Senin e Now FIGURE 1. Profle design tects on de Krction A) MAT TERWNATION, 8) Mar oventar. © forme sor 9 Weeat"tow ensiy, ‘stouenine " FIGURE 2. Locolceinforcement vations. 71 Session 4-B freee onc Force Sensor meior ea) FLusn owPHRACM FIGURE 3. lnteral force sensing methods FIGURE 4. Control panel of Pulster™M machine wih Teendstor™ process moniior (products of Puliusion Technology Diision of MMs). PULL FoRcE lune sPteo Te Tine FIGURE 5. Typical pull force trendsvive PRODUCT: MARINE: STIFFENER b: vane: 04 Brin TE 1:00 pe ae Tint ram INTERVAL + ‘cHonce tan By: ‘Lain 100 ata Pai ‘sree ‘ua summane | | ScneEx axis, = lactnowtoce 11640 Les FIGURE 6. Trendstar display af production profil Forune oI s FIGURE 7. ‘00: of creeis Ream BATH ta a0" 8692 Te de be ae DISTANCE RELATIVE TO OVE ENTRANCE Investigation of pul force components 00: 300, 200: 100: Force, Las eee ae ee ee DISTANCE RELATIVE TO DIE ENTRANCE FIGURE 8. Pullforce ond exotherm conditions dwing shut down ex periment. Sessi08 4.8/8‘46th Annus Conlemnce, Comes tive, The Society of the Fotis Int, nc. ebay 18-21, 1991 ‘Youno Roak Kim ‘StepHeN P. MeCagriy* JEROME P. FaNUcci®* ‘STEPHEN C. NoLEr** An Experimental Study of Compaction and Internal Die Pressure Forces Generated by Reinforcing Materials During Pultrusion ABSTRACT ‘This paper will describe the resus ofa eres of enperiments to measure the behavior of reinforcing materials during different stages of polation [processing Data will be presented showing load versus deformation be- havior of various cloth, mat and uridirectioal materials as they ae sub- {ected to throuph-te thickness compton frees ofthe type experienced by laminates during the wet out and curing stages of &pultrusion process, Data was measured by compressing stacks of various materials under eare= {ally controlled loading conditions and observing the change of fiber volume with load. Effects of parameters soch as testing speed, repeated loading and unloading, material lubrication, material ype, fiber ent tion, multrmteral combinations, stacking sequence and hysteresis Curing loading and unloading will be prevented. Data of this type is extremely ‘valuable for the prediction of pulling flores and for the desig of laminates ‘with specified fiber volumes “Techniques for measuring the continuous distribution of pressure along the interior length ofthe pltusion die wll be also discussed. Data ake ‘sing ACT's disposable pressure transducers during the processing of both ‘thermoses and thermoplastics wil be displayed. The ability to rapidly and inexpensively measure internal die pressure distributions using techniques similar to those now commonly employed by pulruders to make internal he temperature measurements reall stearlines process development e- forts, and provides valuable quality contol fo INTRODUCTION Or rrseson oes tat is receiving ieeasing inert as a method for manufacturing high performance composites is pultrusion. This technology can produce high quality constant cross-section parts continuously at speeds of approximately 1 ‘meteriminute, One modern vaiaton of traditional wet bath pulteu- sion is resin injection-pultrusion. In the injection-pultrusion pro- cess, dry reinforcement materials are continuously pulled from their spools and preshaped using a series of guides, They then ‘move through prcheaters and are compressed as they enter the pputrusion di. Inthe traditional pultrusion process the reinforcing fibers pass through a resin bath prio to entering the die to wet out the reinforements, Injection-pultrusion differs from the traditional approach in that matrix materials are injected directly into the paultrusion die. This greatly increases the range of matrix materials that can be pultreded, and has @ number of quality, health and safety advantages as well. Figures la and Ib illustrate a typical injection-pultrusion system and pultrusion die. “Univesity of Lowell, Pasties Engineering Deporiment, lowell, MA. o1asa **American Composite Technology, 306 Northern Avenue, Boston, ‘MA 07210. L/Sissios 6C In the injection-pultrusion process, monitoring the pressure in- side the die is extremely important for a number of reasons ‘Changes in material volume during cure led to pressure variations ‘within the die which in turn affect consolidation ofthe laminate. A variety of factors including resin viscosity, orientation ofthe rein- forcing layers, volume of fibers, pulling speed and die design in- fluence the pressure profile of the part during processing. Until, recently there has been no sensor equivalent tothe thermocouple that could be used for measuring composite processing pressures fon a local scale. In spite of the fact that failure to apply proper pressure during consolidation can be as damaging tothe quality of composite laminate as poor temperature control, engineers have "until now had to live with lite or no data on the detailed distribu- tion of pressure applied to local regions ofa laminate because in strumentation to economically make such measurements did not exist. Faure to generate adequate consolidation pressure can result in poor fiber wet out with matrix material and a high void content. Both these undesirable cases can significantly degrade the physical properties ofthe composite laminate. ‘The main purpose ofthe study discussed in this paper was the generation ofa data base of compressibility information for a vari fey of fiber reinforcements of interest to putruders. This informa- tion willbe used in the development of tooling and an analytical ‘model ofthe injection-pultrusion process. This paper will also il Tustrate the use of the disposable sensor as a means of measuring, ures developed inside adie during the pultrusion process. In n, sensor data from several other experiments designed to addi ‘measure compaction force versus amount of consolidation of sev- ‘eral different thermoplastic prepreg fibers will be illustrated. In- formation of this type is useful in the design of multi-stage dies of the type commonly used for thermoplastic pultrusion. COMPRESSION STUDY ‘The consolidation of composites has been studied by a number of investigators. Among them, Gutowski et al. [1-3] have pub- lished extensively on the subject. His research has suggested that the fiber network can be modelled as a nonlinear elastic network based on beam bending behavior. Ator below a certain inital fiber volume fraction, V, the fibers carry no load. As fiber volume frac: jon, Vs, is increased, the nerwork can carry a rapidly increasing load. Eventually, the fiber volume fraction of the network ap- proaches a theoretical maximum based on close packed geometry, And cannot increase without an enormous increase in load. In this region, V; approaches a maximum available fiber volume fraction, Vs. Gutowski developed a mathematical expression forthe trans verse stiffness of a bundle of confined, approximately aligned‘bers by assuming that the fiber willbe slightly arched so thatthe applied load comes to rest on the beam section between multiple contact points, and not on the end points. The stress taken by the fiber network in bending is then o where 4, is a constant dependent on the geometry and properties of the fiber network within the ply. Equation (1) assumes some transverse fiber rearrangement during compression. Gutowski ex- pressed that E Aa ® where E isthe bending stiffness of the fiber, and is the typical span lengtivbeight ratio forthe fiber beam network. A computer program was used to find the three variables (4,, V_ and Vs) that Droduced the best fit tothe data, Batch [4] developed a different compression model based on the assumption that the fiber beds act as stiffening non-Hookean springs. This model separates two regimes (Hookean and non- Hookean) depending on the compression behavior. This model is, 0 = KUM, ~ Ve) @ where the fiber elastic constant K is K = Ky for Vj < Vyom (Hookean regime) (4) Ys % nn Ve Va Vy Kak, for V, > Vjam (00n-Hookesn regime) o and the transition from Hookean to non-Hookean regimes occurs at volume fraction Vue ime [me—(S5%P ‘The parameter» isthe fiber packing inefficiency, a measure of| ‘the unattainable volume fraction which is always present whenever fibers cross. Hookean behavior of fiber in low pressure range arises from compression in the interlaminar region. As the fiber network is further compressed, the fiber shows non-Hookean be- havior, Even though these two models require experimental measure- ‘ment ofthe parameters Vo and Vand the curve fiting constants K and A,, the effort required in thir collection is repaid by a beter understanding of the compression behavior of fiber reinforce- ments (COMPRESSION TEST RESULTS AND DISCUSSION ‘Compaction testing was performed using 2 variety of material and fiber forms, Samples made with both single materials and tures of two materials were ested. Materials used for compression test are shown in Table 1. Detailed experimental procedure is described in Reference [5]. Fiber volume fraction was calculated from the measured sample thickness and the weight and dens the fibers being compressed, Fiber densities of 2.62 g/em* for E- lass and 179 glem for graphite wore used for calculations (6). Figure 2 shows the effect of cross-head speed on compressibility From this figure itis seen that as cross-bead speed decreased, the ccurve moved slighty tothe right. Slower speed appeared to allow ‘more time for fiber rearrangement and thus required less load to ‘compress material to a given fiber volume. Figure 3 shows the fesult of repeated compression on the same sample. Tests made us- ing two different material types showed thatthe first run required ‘much more stess to produce a certain fiber volume fraction, par- ticularly in the low stress range(<4 MPa). These results demon- strate non-equilibrium effec related to fiber movement in the ‘mold. If the compression force is applied very slowly, the curve for the frst compression cycle will sift close to the second cycle ‘curve. Note tha repeated compression on the same sample contin- lus to shift the curve to the right gradually. This differs from ‘Gutowski’s results [3] which showed that, while the second com- pression test on the same sample shifted the curve tothe right, the third and subsequent compression tests did not cause any further significant shift. This difference might be due to the use of dry samples for the current experiment, while Gulowski used prepreg, specimens. Use of dry fibers may have resulted in increased fiber ‘misalignment and/or fiber breakage because friction between fiber to fiber contact points would be higher. Dry materials were used for this experiment because they better represent the behavior of ‘materials used in the injection-pultrusion process. Figure 4 shows the effect of lubrication on compressibility. A mold release agent was applied to a sample. During tis test, the lubricated sample showed less inital thickness than the dry sample ‘even before compression. From the figure, it is clear that the lubricated sample was easier to compress. "This experiment in- dicates that lubricating the material eased flber rearrangement at low stress levels, and at high stess levels reduced fiber breakage. Figure 5 shows the effect of fiber orientation on compressibility ‘These results indicate that compressibility is strongly dependent ‘on the fiber orientation. For the case of straight roving, atleast, compressibility soems to be less dependent on fiber’ material stifiess, as demonstrated by the similarity of the curves for straight glass and graphite Figure 6 shows the effect of combining two different fiber orien- tations on the compressibility of the combination. These curves ‘wore generated by testing samples composed of various mixtures ‘of random mat and 0/90 cloth. The two material types were stacked s0 only one dissimilar material interface was formed. It ‘ean be seen from the data thatthe force required to compress a Combination of two different fiber orientations is bounded by ‘curves for the two unmixed materials. ‘Compressibility also changes depending on how the material layers are stacked, Figure 7 shows the effect of stacking sequence ‘on compressibility. From this experiment, it is clear that fiber packing between layers with the same fiber orientation is much ‘easier than packing between different fiber orientation layers. ‘During loading and unloading of samples, hysteresis effects were ‘observed. Figure 8 shows atypical hysteresis during loading and unloading of a unidirectional sample. Hysteresis may be due 10 structural relaxation from fiber reerrangement and fiber breakage in the bundles [MEASUREMENT OF DIE PRESSURE DURING ‘THERMOSET PULTRUSION ‘The use of instrumentation for process monitoring and contol is essential for achieving the consistent quality required in high per- ormance composite structures. In both process development and, {quality contol situations, itis common practice with most pultru- ders to measure temperature profiles along the interior length of a Sisson HE/2die using disposable thermocouples. To make this type of measure ‘ment, a thermocouple is placed within the reinforcements at the die entrance and allowed tobe pulled through the process with the ‘material. Leads are lft long enovgh to connect to areal time data acquisition and display system. When the sensor exits the die, its Teads are clipped at the die entrance end. The thermocouple has ‘become permanently embedded in the laminate, and therefore is rot reusable. In addition the part now contains a flaw, and the Tength of composite consaining the thermocouple is often scrapped. ‘The value of the temperature data in assessing the accuracy and stability ofthe process more than compensates forthe small length ‘of scrap product that is created. Figure 9 shows an example of a temperature profile measured ‘during pultrusion ofa graphite/epoxy part using, & direct resin in- jection system. A cross section ofthe resin injection die is shown ‘on the plot to illustrate the relative position ofthe thermocouple in the tool. The peak die temperature of the heaters in this example was maintained at approximately 170°C. Temperature and sensor positions were logged by computer at 1 second intervals, The ex- ‘thermic reaction of resin cure resulted in an internal product tem- Perature that locally exceeded the controlled heater temperatures, ‘Some solutions © process optimization and production problems with pultruded products may be developed based exclusively on {temperature profile data, but many problems require additional in- formation. A parameter that has a major effect on the quality of ‘cured composite isthe applied processing pressure. The complex interaction of these parameters and their effects on laminate pressure cannot be readily analyzed, nor the results verified, until ‘a method of continuous pressure measurement is implemented. A thin disposable sensor (001 inch thick) developed specifically to ‘measure local pressure in composite processes can be passed through a die in the same manner asa thermocouple to generate a continuous pressure history inside the die. Figure 10 shows a sche- ‘matic ofa disposable pressure sensor. Although the device appears much like a strain gage, ts mode of operation is quite different ‘The sensor is built from two thin layers of material. One layer has an interdigiated grid of electrically conductive ink printed on its surface. This arrangement permits no direct contact between the {wo patterns, resulting in an open circuit. The other layer has a thin film of pressure sensitive conductive polymer applied to its sur- face. The two layers are bonded together in a way that causes the conductive resin 10 bridge the gaps between the interdigiated finers. The device responds to increasing surface pressure by undergoing large resistance reductions that can be easily and re- peatedly correlated to applied force. Since the cost ofthe device is low compared to ther pressure sensing technology, it can be used as a disposable item in many applications. Normal pressure and. temperature limits for this technology are 200 psi and 800°F, although higher levels are possible. The sensor appears 0 eliminate many of the drawbacks of other pressure measurement technologies used in composite manufacturing such as strain-gage based transducers, piezoelectric devices, capacitive devices and fiber optics systems. Figure I illustrates the same epoxy temperature profile shown in Figure 9 overlaid with pressure measured with a disposable Pressure sensor. Forces acting normal to the die surfaces are gen- erated both by compression of the reinforcing fibers and pressur- ization ofthe matrix materials. Thermal expansion during heating competes with volumetric shrinkage ofthe resin as it cures to pro- duce “peaks and valleys” in the pressure profile, The ability to ‘monitor the die pressure during pultrusioa i also useful for moni toring the failure mode of the pultrusion process caused by a die jam, MEASUREMENT OF DIE PRESSURE DURING ‘THERMOPLASTIC PULTRUSION Careful tailoring of the distribution of compression forces ap- 3/ Sisson 4-€ plied to the thermoplastic composite as itis pultruded is required {in order to optimize part quality and production rates. Experience ‘with thermoplastic pultrusion has indicated that maintaining ade- ‘quate through-the-thickness compaction pressure is critical tothe Successful production of well consolidated products from prepreg, and commingled thermoplastic raw materials. Compaction force is ‘controled in a mult-staged die sytem such asthe one illustrated in Figure 12 by adjusting the gaps of the individual stages to obtain the desired stage-to-siage compaction. Knowledge of the force re- ‘quired to obtain a given degree of compaction in a material assists the tooling designer inthe selection of the proper entrance die gap setting as well as the gaps ofthe de stages later in the series. Prior to the development ofthe disposable pressure sensor dis ‘cussed in this paper, there was n0 technique for directly measuring, the pressure history ofthe laminate as it passed dhrough the multi ple stages ofthe pultrusion tooling. Seting the die gaps that control pressure distribution relied primarily on tral and error. The low profile ofthe new sensor makes it possible to pass the gage through the series of dies along with the structural materials by simply lay ing the sensor between layers of prepreg as it enters the die. Figure 13(@) and 13(b) illustrate typical pressure and temperature ‘data measured by passing sensors through an eight die set during the pulirsion of graphite/ULTEM thermoplastic. Final thickness ‘of the pultruded parts 0125 inch. Figure 13(a) shows data from a run made early in the test program. Even with a relatively low fiber loading of 16 pies of prepreg, pressures measured inthe first few die stages are relatively high because the matrix has not yet reached the melting point. In the fourth die the material finally ‘melts, making t easier to compact. The pressure therefore drops significantly. Pressure again rises in the final cooling stage as the ‘material solidifies. The large pressure spike measured in the frst, {ow die stags is undesirable. Applying high compaction loads to the unmelted thermoplastic contributes little to the final consolida- tion of the part, but greatly increases pulling load. A more op- timized process should have # more constant pressure dstibution from stage to sage. Figure 13(b) illustrates a temperature and pressure run made after adjusting processing conditions o attempt, {o more evenly distribute the application of pressure 10 the lami nate. The pressure indie stages 2 through 8 is reasonably constant, except forthe drops that occur in the small gaps between stages. “This pressure trace suggests that a set of more optimized process {ng parameters has been established, and illustrates the usefulness of the disposable pressure sensor in quantitatively converging on ‘the optimum process. MEASUREMENT OF COMPACTION PRESSURE USING ‘A DISPOSABLE SENSOR ‘The disposable pressure sensor has been used in two different types of experiments to measure the force required to compact, various composite aw materials a soom temperature. The fist ex- periment employed a setup schematically illustrated in Figure I. ‘This equipment was designed 10 allow the measurement of th dynamic consolidation response of dry reinforcing material as it ‘was pulled through a tapered de, The est was conducted using dry E-plass 0/90 cloth. The die was designed with a 0.1 inch thickness inet and had a linear taper to 2 006 inch thick outlet. Die length ‘vas 12 inches. 7 layers of the cloth were pulled ffom spools, through the wider die inet and out the nacrower die ext with a roller-pller mechanism. Polling speed was approximately 6 inches/minute. A disposable pressure sensor was fed into the inlet portion of the die along with the reinforcements, ‘Prestute data was recorded as a function of position using @ computerized deta acquisition system. For each pressure daa point, fiber volume fraction vas calculated from the Known areal density fof the material and the local die thickness. Figure 15 illustrates a {ypical result of one test. As the graph shows, allow fiber volumes rear the die entrance the gap is wide and therefore appliespressure to the material. As compaction begins, relatively small changes in pressure produce large fiber volume changes. For the particular material used inthis tes, very little force was needed 10 raise the fiber volume to about 40%. Above this fiber volume, ‘compaction force increases exponentially with fiber volume. The ‘material finally approaches a maximum attainable fiber volume, ‘whichis primarily a function of material orientation and form. At {this point small additional increases in fiber volume require very large changes in compaction force. ‘A second series of experiments was conducted 10 directly measure the compaction force required to compress thermoplastic ‘commingled fiber forms, Experiments were conducted by placing ‘a disposable sensor in the center of an approximately 05 inch thick stack of material, and then gradually applying. through-the- ‘thickness compaction force to the assembly in a hydraulic ress ‘Compaction force was recorded as sensor pressure and total ‘material thickness was measured. Use of the sensor to measure pressure instead of calculating the force from instrumentation associated with the press’ hydraulics or an external load cell ‘eliminated concerns about sample edge effects, simplified speci- ‘men preparation and simulated the techniques that would be uused to measure data in actual pultrusion processing of the materials ‘Results obtained during testing of two different thermoplastic raw materials are illustrated in the following figures. Figure 16 shows compression data for AS4/PEEK fibers stitched into a 4 layer preplied stack with ply orienations of O/4S/90/ ~45. The average fully consolidated thickness of the individual plys, when properly manufactured into a laminate, should be approximately 045 inches. Compressing the cold material to 67.5% of full con- solidation required approximately 100 psi. As the test data shows, ‘compacting the cold prepreg material to levels above approx {mately 68% of final compacted laminate thickness resulted in rap- idly increasing forces. A die designer would probably decide to ‘employ a first stage die entrance gap that would result in approx. imately 65 percent of full compaction based on this data (if material preheating did not occur prior to the die). Figure 17 illustrates results of a similar test conducted using ‘commingled ASA/ULTEM fibers stitched into a 4 layer preplied stack with ply orientations of 0/85190/~45. Fully consolidated thickness of the layer sitched stacks is approximately 0045, inches. Test results show that repeated compression on the same sample did not continue to shift the curve to the right. This difers from the data gathered from dry reinforcing material only. This result is ia agreement with Gutowski’s data, ‘CONCLUSIONS Results ofan experimental and analytical investigation ofthe r- sponse of various dry reinforcing materials have been presented Data showed that compressibility is dependent on 1) fiber orienta tion, 2) stacking sequence, and 3) fiber conditions (whether fiber is dry or wet). This paper has described the characteristics and ap- plication of a new type of pressure sensing device designed specifically for measurement of locally applied pressures in com- posite material processes. Until this device was developed, no cost-effective method for making many of the processing pressure measurements described in the preceding sections existed. The sensor's small size and thickness permit it to be placed directly points where pressure information is dested, rather than following the previously conventional method of inferring pressures from far field measurements. As illustrated in this paper, it is eapable of ‘generating processing data for pultrusion, one of the most difficult ‘composite manuficturing techniques 10 observe directly. This paper also described compaction testing methods using a new pressure sensor, REFERENCES 1. Gutowski, T. GJ. Kingery and D. Boucher. 1986. SPE ANTEC Pro ceding 52:816 2. Gutowski, TG. and 2, Cai. 1988 Manufacturing International 88 Proceedings Volune IV. pp. 13-28. 3, Gutowski, T. G., Z. Cai, 8. Baur, D. Boucher, J. Kingery and S. 3. ‘Wineman, 1987, "he Journal of Compost Materials, 21(6)650-669 4, Batch, G.L. and S. Cumiskey. 1990. 45h SPY Annual Conference. 9°. 5. Kim, ¥.R., S. McCarthy and J. Fanusci. 1990, SPE ANTEC Proceed ings 361232. 6, 1997, Engincered Materials Handbook, Volume 1. Composites. ASM Smeratianal, pp. 46-53. BIOGRAPHIES Young Roak Kim ‘Mr. Young Roak Kim is doctoral candidate i the University of Lowell's Plastics Engineering Department. As part ofthe Doctoral program, he has been doing his internship with American Com- posite Technology, Inc., Boston since January 1989. His thesis in- ‘olved the modeling of the resin flow through fiber reinforcements in the inection-pultrusion die. Mr. Kim was a Research Assistant at the U. Lowell’ Plastics Engineering Department from 1985 t0 1988, In 1983, he received a BS. degree in Textile Engineering from Sung Kyun Kwan University in Seoul, Korea. De, Stephen P. McCarthy Dr. McCarthy joined the faculty of the Plastics Engineering Department atthe University of Lowell in 1984 and is currently a tenured Associate Professor. He received his BS. in Textile Chem= istry from Southeastern Massachusets University and obsained a Masters in Chemical Engineering from Princeton University. He then worked as an Advanced engineer in RAD for Owens Corning Fiberglas in Granville, Ohio. He received hhis Ph.D. in Macro- molecular Science from Case Western University in Cleveland, Ohio. He is currently director of the Mold Analysis Research Consortium at U. Lovell De, Jerome Paul Fanueci Dr. Fanucei is Executive Vice President of American Composite ‘Technology. He began working forthe company fulltime in 1987, after spending the previous year assisting in its formation. His re: ‘ponsibilities include management of financial and technical ac tivities atthe Boston facility. Prior to joining ACT, Dr. Fanucci spent three years asa Senior Technical Specialist atthe US Army Natick Research, Development and Engineering Center. In this position he participated in a number of research projects aimed at the development of composite mobile tactical shelters hardened against nuclear, ballistic and chemical threats. Dr. Fanueci was ‘employed from 1980 to 1984 as a research engineer with Kaman ‘Avidyne, While at Kaman, his work was related primarily to the pplication of composites to military structures. Dr. Fanucci grad uated from the Massachusetts Insitute of Technology's Depart- ment of Aeronautics and Astronautics in 1980, with a Ph.D. in Ad- vanced Structures Technology. He received an M.S. degree from the same department in 1977, He graduated from West Virginia University in ITS with a BS. in Aerospace Engineering. Stephen C. Nolet ‘Stephen C, Nolet isthe Vice President of Engineering at Ameri ccan Composite Technology. He joined the company in 1988. His responsibilities include the development and direction of research Session 40/4programs for the company. Before coming to ACT, Mr. Nolet ‘worked at McClellan Air Force Base in California inthe Advanced ‘Composites Engineering Group. During his four years there, Mr Nolet was involved in the design and analysis of military aiteraft structures ullizing fiber reinforced organic matrix material systems. He developed finite-element models to study both the Static and dynamic response of these structures to operational Toads. He has directed the technical activities for programs such as, the design and production of advanced composite leading edges for ‘AiO ircraf, tooling fabrication for an integrally stifened Gr/BM] stabilizer leading edge for the F-I, and the design, manufacture and testing of a Gr/Epoxy F-4 rudder and F-U1 forward ventral sirake. Mf. Nolet graduated from the Massachusetts Institute of ‘Technology in 1984 with an M.S, degree in Aeronautical En- gineering from the Department of Aeronautics and Astronautics, In 1982 he received a B.S. fom the same department. TABLE 1. Fiber Information for the Compression Tes Materials Orientation Type Manufacturer Steaight roving Unidivecion 1062 Pre Flutty roving Unidiection N/A Scandinavian Glass Fiber inSweden Spunroving __Unidirection GI3SType A Owens Coming (07/90 plain weave cot Blah Style 3 Bean Glas Fiber ne Bidirection HWR240 FRG Random mat Quashisotropie ABM ‘Bean Glas Fiber Ic Combination mat combination’ WOVMAT Bean Glass Fiber Ic “Type 1524 Graphite roving Unidiection M7 Hercules {combination of unidiectional and 0/90 cloth ‘loth racks materiat pultrusion protorming guides polymer Injection engages pulling mechanisms disengaged, TOviNg eutett saw hyaratlle rams finshed product pressurized resin tank FIGURE 1. Typical injection pultusion system. 5 / Session 4-CInjection port thermostats heaters thermostats matrix injection obit “toe ome zone FIGURE 1b. Typical injection-pultusion die ea : TT Tweens) Eo ok coca ra wn20) : @. g é § gs : g 4 é 5 Fite VotumeFacon FIGURE 2 Elec of crosshead spaed on compres FIGURE 4, Lbricoton eet on comeressby Sane niga toe enn ne Dee 8F A ty ening ne cm ~ fim fs Zz ofe mm 2 oft mmm Te a cy = Le seen tae Bobo sam a. ns Fiber Volume Fraction Fiber Volume Fraction FIGURE 3. Effect of repactad compression on a single somple. FIGURE 5. Effect offer orientation on compressibility. Session 4-C 16> 2 4 2 209 oe a so 50781) s0 Position in die x) Fiber Volume Fraction FIGURE 9, Typical pultusion process thermol profile ofa graphite! FIGURE 6. Elect of combination of two diferent fiber orientations epoxy park fon compressibiliy. ° Conductive 2 mbes Pressure polymer Sh a enaine ~ mane Thin film aL Seas substrate g 0 on 2 +f sinoan & ol nace Sandwich Interdigitated wees ose fingers Fiter Volume Fraction FIGURE 10. Schematic of disposoble pressure senor. FIGURE 7. Efect of stacking sequence on compresibity 9 120 ome 2 gs sh sma : zz” = Leet é zo 3 Cte ben 2 :” gz ¢ S i i ¢ 3 2 * 8 2 3 °9 258075 100135 150 Position (em) : eS, eas oe a FIGURE 11. Graphitelepoxy por processed with pressure sensor Fite Vine Fraction nd thermocouple. FIGURE 8. Hysteresis during loading and unloading, T1Sess10N &-CIndividually eated segmented dies > pusting force FIGURE 12. Typical thermoplastic mli-stoged die system ns. ‘Temperature CF) temperature * T t i g y Position (in) @ Os G0 Position (in) co FIGURE 13, Pressure proies fom tharmoplostic process develop- ‘ment runs. [o] Uneven pressure dstibuton couses poor consolido Tro. (b] Even pressure distribution reulsn good quay pom. FIGURE 14, Experimental setup for measurement of consolidation pressure ina simuloted pulusion de, Pressure (psi) FIGURE 15. Compaction dota using 0 disposable senso simulated pultusion die, z 5 i 90 lt - 0 on © o ° 3 oe os Fiber Volume Fraction Fiber Volume Fraction FIGURE 16. Compression behovior of ASA/PEEK commingled form. Pressure (ps) Fiber Volume Fraction FIGURE 17. Compression behavior of ASA/ULTEM commingled form, Sessions 4.0846th Annual Ceoleere, Composites Insite, The Socay of tho Plas nd, ne. febrery 18-21, 1991 PC. Brant M. PoLLaRo® Analysis of Processing Parameters for Pultruding a Highly Reactive Novolac Epoxy-Based Vinyl Ester Resin apsTRACT ‘A stitial experimental design combined with a mathematical model ofthe puliosion process has ben used to evaluate the eles of various fetalysts onthe procesing parameters and the final quality of composites ‘made witha novolac epox-baed vinyl sir resin, Pricule attention has been focused on eliminating interior cracks in thick composites. The model has guided process development by estimating the preheater paver output ‘nd di eater st poi temperature required to minimize thermal gradients inthe pan wile maximizing the final extent of cre inthe resin. Ith also heed seren new resinicatyst systems for fbrication of pats with com. plex georeties. The results ofthese analyses indicate tat: (2) the bert uring profiles are achieved when low coneentraions of the instr PERKADOX® 16 are used inthe eesia formulation; (b) ne speeds mist be kept between one andtwo fet per minute when paltring thick pars with avery reactive resin (6) he preheater mus be elated #0 tht ight con two of ts power ouput is minained at all mes; and (d) die design and feinforcement ype are imporant variables for eliminating parting line eles regardless ofthe shape ofthe par. INTRODUCTION Comins auth of the pltrsion indy can only be achieved by the fabrication of costeffective and high-quality composite parts that can rival alternate products, Dow resources hhave been dedicated to helping customers improve their processes by providing them with product and process information. Along with an increased understanding of the basic processing fundamen: tals, there must be a sustained effort throughout the pultrusion in- ‘dustry to optimize processing parameters to continuously improve ‘composite performance ‘ery lite published information exists to assist the pultruder in selecting the optimum formulation for a specific part design and application, Many fabricators use certain catalysts and resins for ‘certain applications without thoroughly understanding why these formulations are effective or how they can be improved. The pur- pose of this paper isto evaluate the effects of various combinations ‘of peroxide catalysis on the processing parameters of a commercial Dultruder such as line speed, preheater power output and die heater temperature. Initially, statistical design techniques have been employed to screen potential catalyas combinations for highly reactive novolac epoxy-based vinyl ester resin using SPI gel test. A ‘model ofthe process has been use to suggest the parameters nec- essary for processing the best candidates to produce a crack free 1 composite rod. With the combination of experimentation and ‘modeling, optimum parameters have been identified that produce “Dow lost, 1 / Session 4-D quality composites as measured by absence of cracks, degree of fin conversion, composi lass transition temperature (1) and surface smoothness EXPERIMENTAL DESIGN ‘The statistical design used in this study consisted of 10 ini- ators as the independent variables and the exotherm rate as the ‘only control variable. The novolac epoxy-based resin sytem used was the DERAKANE* 470-36 vinyl ester resin." The temperature rise due tothe excthermic reactions and the gel time were used t0 evaluate each of the combinations. Table 1 summarizes the results from the SPI gel tests for the various initiator combinations. Gel Aimes were generated from formulations containing no filler. From, these screening tests, promising catalyst systems were identified. ‘he effects ofthese catalysts on the curing behavior of composite parts were established by various pultrusion runs. Samples were pultruded using formulations identified by the initial tests at dif ferent line speeds, preheater and die heater set points, and type of reinforcement. The formulations of these runs are shown in Table 2. The glass transition temperature (7,) of selected samples was ‘obtained by Differential Mechanical Analysis (DMA). After each scan, the samples were scanned agai to obtain an indication ofthe degree of cure EQUIPMENT {Al ofthe pultrusion trials were conducted on a Model TM $70 ‘machine manufactured by Morrison Molded Fiberglass. Thee dif- ferent steel dies were used in the experiments, all made of stel with a chrome-plated interior cavity. Generally, 16"long, 1000- ‘watt electrical resistance heaters in pairs were atached directly oa the top and bottom ofthe die, Thermocouples were imbedded into, the die to monitor its temperature with the control thermocouple for each heated zone located near the midpoint of each heated se tion. Additional 30-gauge type “J” thermocouples were passed ‘through the die inside the composite to determine the temperature and location of the peak exotherm temperature at various radial positions in the pat In one case, a 48"long die was used to produce a cylindticat part of 1"-diameter made with unidirectional glass rovings. One pair of heaters was used to contol the temperature atthe front of the die with its set point located approximately 7.5" from the die entrance. A second pair at 30° from the die entrance was used to "rademark of The Dow Chemical Company.‘control the middle portion of the die. Ten type "I" thermocouples, ‘mounted into the die measured its temperature profile. A Thermall, dielectric heater, model 50/67 CONV/I00, was used as a preheater for fabricating the thick pars. Inthe second phase of the study, # 39°-long die with a parting line located at a midpoint in the die cavity (see Figure 1, design "8? was used to produce laminates made with unidirectional rein- forcement as well as several combinations of unidirectional and spun roving, The cross section ofthe composite part was an Tl mm. (0:43") square. Two pairs of heaters were used at postions starting from 1.5” and 18:5” from the die entrance respectively. The 1oca- tion of the control thermocouples was 25 em (986°) and 74 em (9.2) from the die entrance for the two heating zones. Pultrusion, ‘wils were also conducted using a 30"-long die which produced a ‘part of rectangular cross section of approximately O.II” x 1.5". ‘This die had a parting line located along the top commer of the in terior cavity (see Figure I, design “B"). A pair of heaters starting from 2.75” from the die entrance with @ control thermocouple located 1.25” from the die entrance maintained the temperature in the die. Unidirectional together with spun roving reinforcement was used, No preheater was used for pultruding these thin sec- tions. ‘THEORY SPLGe ‘The rate of temperature increase was derived from the parame- ters of the SPI gel test as follows ER = (PET ~ Bath Temp + 10°FV(IPE- GD where ER isthe rate of temperature increase ("Fimin), PET is the peak exotherm temp. (°F), TPE the time to peak (min.), and GT is the gel time (min. Model ofthe Pltrusion Process ‘A model fr the process to deseribe the changes tha occur inthe ‘composite part as it moves through the preheater and die and also to monitor the temperature distribution inside the die. Therefore, two distinct sets of equations describe this process that are linked the boundary condition atthe die/part interface. In this model itis assumed that: (1 the sytem has reached steady-state; 2) only the velocity component parallel to the flow is non-zero; (3) axial difusion is negligible by comparison to axial convection (assump- tion valid since the Peclet number is greater than 100); and (4) the ‘composites in contact with the die at all times. These assumptions mean that each cross section of the composite experiences the same changes regardless of the time it enters the process Compostre pag ‘The diferential equations used to describe the mass and energy balance for the composite part as it passes through the pultruder is constant, v, = 0, 4 = O(continuityy 2) aP/ar = 0, aP/8z = 0 (motion) e eGaT lac = kirBlar(rOT/0n) + @EAHR, + kd*T180 (energy) ® aC ae = ER, (continuity of species o where R, represents the rates ofthe chemical actions and AH, is the heat of reaction. Expressions for the reaction rates have been presented elsewhere [i] Iti assumed that the composite enters the preheater at room temperature with @ uniform velocity profile and ‘concentrations at C,». The power absorbed by the heated body in the preheater is [2]: = 556-0 -f- Ee tans o where Q is expressed in Wem, fthe frequency of the alternating field in Hz, E the electric field in volts/cm, andthe product e, «tan Bis the “loss factor” The intensity ofthe electric field depends on ithe voltage, the material being heated, and the gap between the electrodes in the heater E=Vid( + 6 denldy* o ‘where Vis the voltage, dis the thickness of the material, and da is the thickness of the layer of air between the electrodes, It is ‘assumed that the material is heated uniformly. This is an excellent assumption because the penetration thickness for the frequency of typical RF heaters is in the order of several meters. Natural con- vection takes place atthe surfaces ofthe composite part that are ex- posed to the surroundings: g= Uw ~7) 6 ‘where 4 is the area exposed to the environment and U can be est- ‘mated from the Nusselt, Prandtl, and Grashof numbers (3): Nu = (Gr + Pry o with Nu = UL/k, Pr = wy, and Gr = L'g'gG Tip. For air above horizontal surfaces with Pr = 07 and Gr in the order of 10, a = 054, B = 0.38, and m = 025 [3]. The temperature dif. ference between the heated die and the air above it varies from 50 to over 100°C and, therefore, an average value for U can be used. ‘Atte interface with the die, the temperature ofthe part and the die are taken to be the same, and therefore, the heat fluxes have to balance: Taw 0) Gere = ae OF KOTIBY = hyuBTuBY a ‘Temperature Distribution inthe Die ‘The steady-state 2-dimensional heat conduction equation in car tesian coordinates describes the temperature distribution in the die Paddy + PT uid = 0 «2 subject tothe boundary condition at the interface with the compos- ite part shown in Equations (10) and (I). Atte interface of the die ‘withthe heater, Tau = Tuan and at the regions that are exposed tw the atmosphere, q = UAT, ~ Ta RESULTS AND DISCUSSION In atypical pultruger the wetted fibers move through a prehester (Gf thick sections are fabricated) and, after the gap, they enter a heated die. Each cross section of the composite experiences the Stssion 4-0/2same changes, provided the process has reached steady-state ‘Therefore, one only needs to consider the curing characteristics of, a single section of the part and observe its behavior as it moves through the process line, While inthe preheater, the temperature in ‘the part rises almost uniformly, with the surface of the material at slightly lower temperatures due to heat losses tothe surroundings. After the part leaves the preheater it cools down before it stars 10 ‘neat up agaia as comes in contact with the die, Inside the de, its ‘surface temperature increases and it sats to react. AS the resin ex ‘therms, heat is tansferred into the die and is also conducted towards the center of the part. Layers of the prt adjacent to the surface start to react, which causes more heat to be released into the system. The ast point o react i the center ofthe pat. The heat released from the exothermic reactions forms a thermal wave that Stans at the composite/die interface and propagates tovards the center ofthe part. Due tothe low thermal conductivity of the com- posite it is not easy for heat to dissipate. High temperatures are Benerated at the center that create large thermal stresses which ‘cause the part to crack in a star-like failure ‘A typical curing strategy inpultrusion is to hest the composite in the preheater to high enough temperature so thatthe center of the part starts to react first (i. The thermal “wave” propagates from the enter towards the interface with the die. Such a curing profile is desirable because the heat can dissipate into the die and does not cause extreme temperature gradients in the part. The shape of the temperature profiles is controled by the amount of heat absorbed by the composite inthe preheater and the temperature distribution inthe die. Therefore, the preheater must be calibrated accurately ‘and the die heater set points must be controlled at all times. ‘The “optimum curing strategy” cannot be applied in the case of the DERAKANE® 470/36 vinyl ester resin and tertiary butyl peroctoate (TBPO) because the operating window forthe preheater ‘output is very narrow. The resin Isso reactive that fit is heated in the preheater to a high enough temperature to start curing from the center, it starts to gel outside the die. If itis proheated to a few degrees lower, it stats to cure from the surface and creates «high {temperature exotherm at the center. The maximum temperature oe ‘curs a the center of the part as soon as it leaves the preheater. This, {emperature is reerred to as the "core temperature” Initial pultrusion runs have shown that indeed this system pro- duces a large and rapid temperature rise that causes interior crack- ing in thick parts, The temperature profile for a 1” diameter rod fabricated with this formulation is shown in Figure 2. This i @typ- ical system tha illustrates the rapid exotherm in the center, ic, ‘maximum temperaure of 383°F with an exotherm rate greater than 200°F per minute. Generally, formulations containing these types of resins ean be processed easily without cracks ifthe rate of temperature rise is below 00°F per minute. Ifthe rate of empera- ture rise is between 100 and 200°F per minute, the preheater and die set points must be adjusted carefully to avoid large thermal gra dents in the pat. It has been observed that if the exotherm rate is, ‘greater than 200°F per minut, the operating conditions cannot be adjusted to produce crack-free pars ‘Various catalyst combinations were evaluated in a preliminary study to select a stem that can be used to pultrude parts made DERAKANE® 470/36 vinyl ester resin, The resuls indicated bsed on the SPI gel tests, the catalyst system containing PERKADOX 16 and cumene hydroperoxide (CHP) provided the best combination of resin stability and reactivity Fabrication of Thick Composite Parts ‘The PERKADOX I6/CHP initiator systems used in the ex- perimental design study was selected because ofthe low decompo- sition temperature ofthe PERKADOX 16 and the broad exotherm ‘curing characteristics observed in systems containing CHP. Due 10 its novolac epoxy backbone and the high level of carbon double 3/ Session 4D ‘bonds, the DERAKANE* 470/36 vinyl ester resin polymerizes rapidly with a large energy release. Rapid cure is necessary 10 achieve fast line speeds, but there is also the possibility of cracking in thick sections due t thermal stresses induced by the fast ter perature rise in the composite, Therefore, the concentrations of each initiator must be carefully balanced so that they would pro- vide enough energy to activate polymerization ofthe resin without ‘causing the curing rate to go out of control. The pultrusion process model was used t0 estimate the initiator Concentration, preheater power output, and die heater temperature to achieve optimum curing profiles. Initial model results suggested that alow amouat of PERKADOX 16 should be used in order to avoid high temperatures in the interior of the part. Based on sug [gestions by the process model, various pulirusion runs were per- formed using the PERKADOX I6/CHP combinations shown as runs 1, 2 and 3 on Table 2, Numerical simulations further sug: ‘ested that, due tothe low staring temperature and small amounts of the PERKADOX 6, the overall temperature rise would not be high enough for CHP to decompose and contribute 10 the resin, cure. These resulis were confirmed by pulirsion trials which duplicated previous runs containing both initiators but with only PERKADOX 6 asthe initiaor (runs 3 and 4 on Table 2). Temper- ature profes from both trials demonstrated thatthe model was ac~ curate in its predictions. ‘As an example, temperature profiles as a function of axial posi- {ion at to radial poins are shown in Figure 3. The abscissa denotes the distance from the entrance tothe preheater to the exit from the die. For the first 17" the composite isin the preheater. In this re gion the temperature rises almost uniformly. The part leaves the preheater and, consequently, cools down before it enters the heated ‘ie after approximately 17” more. As the composite enters the hot dig, its surface temperature increases and it stars to reat (surface 1). As the resin cures, a thermal wave is crested that propagates toward the center of the composite. The resulis indicate that both ‘the maximum temperature reached and the rate of heating near the center ofthe partis acceptable for these conditions. “Temperature profiles from runs 1 and 4 from Table 2 are shown in Figures 4 and 5, respectively. In all case, the temperatures along the wall show two peaks that correspond tothe two heating zones, in the die. The resin starts to cure in the fist heated region and cools down before the part enters the second region, which is Kept ata higher temperature. As the initiator level is increased, the peak {temperature a the first heater region increases and, therefor, the distinction ofthe two peaks diminishes. The shape ofthe exotherm, temperature profiles in the interior of the part i similar in all ‘eases. The differences are that as te inital catalyst concentration jncreases, the maximum temperature at the center of the partis higher and the location of the exotherm is closer to the die en- trance, These profiles show no exothermic spike, unlike the pro- files generated in Figure 2. This gradual heat release reduces the ‘thermal gradients within the part and eliminates eracking Figure 6 compares the experimental profiles with model predic- tions for the formulation shown as run 3 on Table 2. The model predicts the overall behavior of the system, especially the tempera- ture profile along the wall of the die and the onset of the exothermic reactions atthe center of the part. The model predicts a decrease ‘of the core temperature afer the part is cured while data indicate thatthe temperature drop is minimal at that stage. This discrepancy ‘cam be attributed tothe boundary conditions atthe interface ofthe part withthe die. The model assumes that the composite sin con= {act with the die at all times, and therefore, the die acts as a heat, sink at that region. In practice however, the composite shrinks ‘away from the die o that the heat transfer from the hot part towards the cooler die slows down, The predicted maximum temperature rise close to the center of the partis slightly higher than observed. The difference is probably due to the difficulty of the computer code to integrate the very “siff" differential equations at this re- gion. The model results are used to screen various formulationsand processing variables before any experiments are carried out, $0 thatthe range of the possible conditions is narrowed down. Fabrication of Thin Composite Parts ‘Thin pars ae easier to pultrude because the heat that is gener- ‘ated from the curing reactions can dissipate into the die. High- temperature initiators and celatively large amounts of them can be used in the resin formulation to achieve high line speeds. For this reason, tertiary butyl peroctoate (TPO) was the catalyst selected to pultrude an Il mm square cross section part made with DERA- KANE 470-36 vinyl ester resin, TBPO blended easly into the resin and provided for fast cure in the die as well as long potife. ‘Table 2 contains the formulation used to pultrude this pat at line speeds up o4 ft minute. There was some minor interior eracking, but this should not be & problem for producing thinner parts of 25” or less, Figure 7 shows temperature profes throughout the Jength of the die at wo postions in the cross section of the pat. The data demonstrate thatthe resin sytem is fast enough to fully react inside the di a line speeds up o 4 f./minute. Die Design and Reinforcement Selection ‘Two die designs with diferent parting lin location were evalu- ated for pultruding a rectangular prof Die design “B" (Figure 1) has the parting line along the top comer ofthe die cavity, which is ‘ahigh-stress position. This design create a sharp corner along the top ofthe cavity because ofthe intersection of the horizontal and vertical surfaces. Ths die design creates parting ine defects on the surface of the composite regardless of the reinforcement used. In ‘one trial, the reinforcement consisted of SO% spun reving EC 4000, ‘TX K247 from Vetroex with the rest being unidirectional PPG HYBON 2070 112 yield glass. The fiber configuration was such that all ofthe spun roving was in contact with one die parting line and the opposite side was in contact only with the unidirectional roving. Surface defects were sil visible, although the side with the spun roving had less severe defects than the other side. The spun roving appears to provide a scrapping action as it moves through the die which helps to reduce resin build up along the parting line and along sharp-angle regions ofthe composite. The spun roving ‘may also provide additional reinforcement along the corner of the ‘composite where stresses are high and where resinrich areas may exist. ‘Bulked roving from Owens-Corning Fiberglas was also evaluated for its ability o reduce and eliminate resin build up on the compos- ite surface, This roving was nota efficient as the spun roving in re- ‘moving defects under any conditions, Parting line defects were ap- proximately the stme with this type of reinforcement as with “unidirectional roving. ‘The second ype of die design evaluated is designed as "A" in Figure 1. This symmetrical desig has the parting line atthe mid- point between the upper and lower die halves. This serves two pur- poses: I) the parting line is removed from the high stress corner re- fon of the cavity, and 2) the interior corners of the die can be Tachined with a sight radius. This design reduces the area where resin can accumulate since the fiber loading can be low. Low fiber ‘content along corner regions can clog the parting line, solidify as, the resin cures, and can then degrade the material by chipping the surface or adhering tothe part as it passes by. Utilizing two or three strands of spun roving along each parting line with a die hav- ing a symmetrical design eliminated parting lie defects ‘Glass Transition Temperatures of Pltruded Samples ‘The glass transition temperature (7,) of selected samples was measured by two consecutive scans using DMA. The first scan ‘gave the T, ofthe sample and the second the T, of the same sample after the post-cure. Table I contains the results from these anal- yes. The degree of cure was calculated as the ratio of the glass transition temperatures of the specimen before and after the post ‘A high degree of cure was achieved for formulations 1, 3, and 4 with only a slight decrease for formulation 4. The average T, for Formolations 1-4 is 368°F. The T, by DMA is substantially higher than the 7, from a DSC analysis'on just the neat resin, which is ‘generally 300 to 308°F. The J, of the composites containing TBPO. land pultruded at a line speed of 6 feet per minute is 387°F, in- dicating a high degree of resin conversion. Model simulations also, predicted conversions of approximately 95%: ‘CONCLUSIONS 1. Proper catalyst selection and process control are necessary t0 fabricate composite parts of thick cross section made with highly reactive novolac epoxy-based vinyl ester resin. 2. Thin parts can be pullruded using these resins with higher- temperature catalysts and up to line speeds of 4 feet per minute 3. Die design and reinforcement selection are important vari- ables in eliminating parting line defects and improving the ur face quality of the composites. 44. Predictive ‘mathematical models combined with statistical design techniques are useful tools in evaluating and optimizing processing parameters in pultrusion REFERENCES, 1. Buck, H. J, L. T; Blankenship and P_. Bryan, 1989. "An Optimal Caring Approach for Puluded Vinyl Ester Pars? Proceedings of the ‘ih dnnual Confrence, Society of Plies Industry, Session 4C- 2. Oru, M. 197, Blecric Process Heating. Columbus, Oto: Battelle Pres. 3. 1973, Chemical Engineer’ Handbook. R. H. Perry and C. H. Chilton, Editors Chapter 10, Sth Edition, New York: McGraw-Hill BIOGRAPHIES PC. Bran P.C. Bryan is a Research Enginecr in the Reaction Molding & Composites Laboratory of Dow Plastics. He received his BS. degree in Mechanical Engineering from Lamar University and is, ‘currently responsible for pultrusion and corrosion-resistant resins. M, Pollard 'M. Pollard is a Research Engineer in Resins R&D of Dow Plas- tics, She received a BS. in Chemical Engineering from the University of Houston and an M.S. in Chemical Engineering from ‘Washington University. Her research involves modeling of tech- niques for fabrication of composite materials, Session 4D /4crn Tanne Gp oy Hem xo ae Mo is j= 5 SO om fae 28 Bo = . 100 se me 3.90 ° 8 16 cs 36 a a Soom cats on do eo ™ oe “S wee oe FIGURE 2. Axicl temperature profiles: ered oF three radial posi- a o6e 2 ae 298 tions ino 1” diameter composite rod. Formulation: | phr TBPO, 15 ose aus asus 3.90 ‘hr CaCo, as file, | ph Onholeum 162 o¢ mold release agent, 70, ‘wie glass fibers. Processing conditions: lin speed: | Winn, core amperaive: 200°F; die heoter set point: 225¢F TABLE 2. Pulrusion Formulations ‘rose section 1° olan, mod sam square a0 Temperate (F) begree of cure, (8) 97-2 —— std ant ° 20 0 0 0 Distance from preheater entrance fr) FIGURE 3. Model predictions forthe temperature distbution in o Parting ine 1 compote ed aly = 03" ac = Ties Foriion: 04 7 X 16, 15 phe filer, 70 wih glo bers. Procesing con- cavty ‘tion: line speed: Iflin, cove temperate: 200°F, die heater set (0.6 x0.5) points: 230 ond 260°F i 3 Tena cavty 0.540.117 Design FIGURE 1. Schematic representation of die designs, ° a a a ) Citance fram ce entrance Ga) FIGURE 4, Axol temperature profiles gathered ot two radial pos: tions na 1" diameter composite ro forthe same locations, formule tion, and processing conditions es in igure 3, bul veth 0.75 piv CHP ‘ond 0.5 phr P-9 08 mold release agent. The llr is ASP-400, $/Sission 4D‘Temperature F) Distance fam de entrance fn) FIGURE 5. Avl temperature prtiles gathered ot wo rod pos fons ino I” damaterconposte ed et = 0.5" andr = 6188" Femoloton 0.8 pr PEREADOX 1,15 phe CHP, TS phil, 05, phrmol legs ager, 75 wb gs lp. Pecensng conction fn speed Iimins cor lemperote: 10°F, ci eater set pont 230 ord 200° 0 a a a ) Distance from de entrance (a) FIGURE 6. Comparison of model predictions with experimental date for oxiol temperature proles at wo focal postions (° = 0.5" fond r = 0.125") no |” diameter composite rod. Formulation; 0.6 ‘hv PERKADOX 16, 1.13 phr CHP, 15 phr ASP-400 as filer, | phe Ortholeum 162 2s mold relecse ogent, 70 wi glass fibers. Process. ing conditions: ine speed: | Winn de heater set pols: 240 ond 20°F. Nol. The model does not account for hemold release ogent forthe CHP. ° 70 20 0 40 Distance trom de enrance (ih) FIGURE 7. Asiol tempercture pros gathered ot hwo postions in en TI mm square cose secon composte por, Formulation: 2 hr ‘BPO, 20 ph COCO. oiler, | phv Onhotoum 162 os mold release gent, 74 wi8e gloss bers. Procesing canations: ine speed: 4 fin, core temperohre: 200°F, die heater st pln. 300° Session 4-D/646th Annus Cenlamncs, Compostos hati, The Society of he Poss Indy Ine. February 18-21, 1991 M. W. Kuerr® EA. MaRrINe* Mechanical Property Relationships of Pultruded Fiber Glass Reinforced Plastic (FRP) Unidirectional Composites ARSTRACT Palirason has been cite by the SPI as the atest growing RP segment ‘Mechanical propery databases which ean be readily accessed ty design engineers and puliriders are growing. However, the correlation between {he properties and the actal fae mechanisms forte puluded compos ite are not completely understood. This paper addresses some ofthe funda ‘mental questions eegurding the interrelaionships of mechanical properties forthe purpoce of aiding pultrders and design engineers. Uniiections composes were police fm a rigid isophhale polyester rein and Singleend ler glass eovings with various sizing chemistries. Shear, flex: tral tensile, and harness properties were measured and analyzed by sa Uistical methods. Resuls showed a srong correlation between shea (and ‘leara) properis andthe degre of cue forthe composite In const, no significant effects were foun tobe duc w the glass ber esi strenghs ‘with ether shear or flexural properties forthe range of glass conten sues. INTRODUCTION the behavior of a composite depends on the physical prop- erties ofeach ofthe components that form the structure. The ‘compatibility between the various components and the orientation fof the reinforcement are important in determining the types and amount of stress the composite can withstand. Thus, the proper choice of reinforcement is critical for producing pultruded com- ‘posites that are required to meet strict specifications. Fiber glass rovings are preferentially used in the pultrusion process because they are low cos, high strength materials that canbe tailored to be ‘compatible with most matrix resin and process conditions. In addi- tion to affording lightweight composites with exceptionally high Jongitudinal strength, pultruded FRP also offers excellent chem cal and electrical resistance properties. ‘The mechanical property contributions ofered by the fiber glass roving component in pultruded composites are not fully recog- nized. Most pultruded composites consist of a core of rovings sandsviched between a combination of mats, Mechanical property data bases have been published {1,2} for these moving compos~ ites, but they have been restricted to variations in either the resin ‘or the glass roving content. Data summarizing physical and me- chanical properties for an all-roving pultruded part are scant (3.4, and these data provide litle insight 0 the contributions ofthe glass ber in the finished composite. The current study’s objectives are threefold: Q) determine the key physical properties of fiber glass rovings and their relationship to the mechanical properties of the final composite; (2) begin to develop an understanding ofthe fail *PPG Industes, nc, Ptsburgh, PA 1/ Session 4-6 ture modes of pultruded composites; and (3) reduce testing time for new roving product evaluation EXPERIMENTAL FFor the purpose of this study, 1/2” wide by UB" thick unidiree- tional composites were made on a Pulstar 80 pultruder. The heat- ing platens were set at 250°P/275°F (Zones 1 and 2, respectively), and pull rate was adjusted for 26°/min. Each composite was con: structed from an isophthalic polyester resin mix and 1 tows of a 1I3-yield direct draw roving. The resin formulation and physical properties are given in Table I ‘A total of 16 distinct roving products were used, each difering ‘only with respect to the “sizing chemistry” Filament diameter, umber of filaments, and glass composition were identical. The various sizing chemistries selected were designed to exhibit a range of plas fiber strengths and shear properties. ‘The composites were tested for tensile, flexural, and shear prop- certes parallel tothe direction of pull. Ail tests were performed on Instron testing equipment according to ASTM procedures (Table 2), and resuls are tabulated in Table 3. Glass strengths were ob- tained using the ASTM strand tensile test method utilizing the ‘same resin (rigid isophthalic polyester, no filler) as that used inthe poltruded composites. In addition, a second set of strand tensles ‘was prepared utilizing a higher elongation resin (flexible isoph- ‘thalic polyester). Glass filament stengths were determined from ‘equipment and procedure described by Cameron (5} afer the fil mens were carefully removed from the roving bundle. Barcol hardness values reported are averages of 10-12 readings ‘over a 2-f. length of composie in accordance with ASTM. Degree of cure vas evaluated on Rheometrics RSA II DMA and Perkin Elmer Series 7 DSC units. Infrared spectroscopy (IR) was per- formed with a Perkin Elmer 1750 FTAR using standard diffuse reflectance equipment. RESULTS Figure 1 summarizes the methods employed to measure tensile ‘strengths for rovings with different sizing chemistries. The glass filament tensiles were the highest at 317 ksi. The sizing had a dra- matic effet on the filament tensile with values ranging from 88% to 63% of pristine strength. The average pristine strength for E- lass fibers is 500 ksi (6) ‘Sand tensiles (exible and rigid resins) and composite tensiles were progressively lower at 310, 256, and 204 ksi, respectively. ‘The smaller effect of sizing andthe lower average strengths are in line with the decreasing % elongation forthe corresponding resins(able 4). The data clearly show thatthe final composite tensile strength within the range of glass coatent evalusted was primarily Timited by the low clongason of the resin sysiem, not glass strength Figures 2and3 show the eft of shear and flexural suength as ‘ Tunetion of Barcol hardness fr rovings with diferent sizings.In- plane shea, shor beam shear, and flexural (16: spanto-depth) Strengths showed the most dramatic effect. ‘The Barcol hardness test has been successflly used for many years to determine the extent of cure in FRP in the absence of more ‘expensive and sophisticated thermal techniques, such as DSC and DMA. DSC analysis of the composites showed enthalpies that were identical, even for samples having differences in Barcol of 12 Doins. DMA’ likewise shoved no diferences in Ty or storage Modulus (E’). Analysis by diffuse reflecunce IR did show ditferences in the level of unsaturation or deree of cure. Expei- seat Nos. 14 and 16 exhibited the largest differences in Barcol hardness and mechanical properties and were therefore used for the IR analysis The degree of cure was inferred from the differ ences in the vinyl CH and aliphatic CH suetching regions ob- tained by integrating the appropriate absorbances. The (C—H) nd {CHa aio for composie No. 1 was measured 1% higher than that of No. 16 implying that No. 14 has a lower degree of care. The discrepancy between IR and Barcol hardness with the thermal esl is de to the sensitivity of detection for each ofthe methods. Depending on the incident ange and the substrate, in- frared spectroscopy 18 capable of measuring CH stretching fe- quencies within 25-062 micron of the sample surface, For the Present samples, this includes bot the ulk resin and the interface Fegion between the glass and resin. Because the sizing was he only ‘arable, the higher level of unsaturation detected by IR analysis is Inost likely to be localized ator near the interface. The Tower degre of cure atthe interface repion i consistent with the lower shear properties and Barol hardness. DSC and DMA analysis ap- parenly reflected only the “bulk” cure forthe composite studied here The equivalent enthalpies for the composites are consistent with the fted process parameters (@g., die temperature, pll Speed, and resin system) used to prepare the samples. Therefore, differences of unsaturation cbserved for Nos. land 16 suggest Aierenes in the degree of cure, predominantly a the interace Siang chemistry seemingly controled the degree of cure at thei terfce and hence limits the shear and flexural properties, whereas the process conditions contraled the bulk cue forthe composite “The shor beam shear values averaged 22% higher than those of incplane shea, but the slopes forthe two methods were identical “The lover values fr in-plane shear result from sess concenta- tions atthe notch tps 17}. The minimal sample preparation re- ‘quired and the eae of testing short beam shear samples make this method more attractive for unidirectional composts, Flexural strengths with span-to-deph ratios of 32:1 or less are ‘dependent predominantly on depre of cur. As the spanto-depth {alo was increased from 1610 32:1 to 40:1, diferences between the various sing chemistries became less important (Figure 3). At 2 span-o-Septh ratio of 48:1, flexural suengths were vitally in- distinguishable. A. plot of flexural strengths vs. span distances five in Figure 5 shows strengths decreasing with increasing span distance. This is most likely due to an increase in probability for flaw distribution with the increased length of the specimen. Although all samples (excep for Experiment Nos. 1to 4 using @ 16:1 spanto-depth) appeared to fai a teasile mode, there was & negligible corelaion with glass lament strength CONCLUSION ‘The physical properties of fiberglass and mechanical properties of the finished composite are strongly influenced by the sizing ‘chemistry. In this study, variations in the sizing chemistry pro- ‘duced glass filament tensiles from 63-845; ofthe pristine strength for E-glass fibers. Less dramatic effects resulting from sizing ‘changes were observed for strand tensile and composite tensile ‘The elongation characteristics ofthe resin system dicated the ulti ‘mate tensile strength achievable witha glass reinforement. For the low elongation resin used, initiation of failure occurred in the ‘matrix, and hence the fiber glass was not subjected to its ultimate failure strength ‘The sizing also controlled the degree of cure atthe fber/resin terface. The “bulk” cure for the composite appeared to be con- trolled by the process conditions (ie. die temperature, pull speed, and resin system). The degree of cure for the composites had negligible effect on the tensile strength but showed a pronounced effect in flexural (span-to-depth ratio less than 32:1) and shear values Flexural strengths with span-to-depth ratios of 32: or less were found to be dependent on degree of cure. As the span increased {6:1 to 32:1 to 40:1 t0 48:), diflerences between the various sizings became less important. At spans greater than 32:1, flexural ‘strength values decreased with increasing span. ACKNOWLEDGEMENTS. ‘The authors are very pleased to acknowledge the help of the fol~ lowing Fiber Glass Division personnel of PPG Industries, In., ‘whose kind support has made this paper possible: W. R. Pish and M. C. Peconi for performing the mechanical property testing, MC J. Famish for conducting DSC and IR analysis, and Drs. P. Gaa, D. E. Dana, and N. Raghupathi for proving valuable tech- nical assistance in preparing this paper. Lastly, the permission of PPG Industries, Inc., to publish this paper is also gratefully ac~ knowledged [REFERENCES 1 McQuarrie, TS. and JH. Hickman. 1987. "The Pulte’ Handbook to Resin Selection” 42nd Amol Conference, SPI Reinforced Plasiee\Composiesinstiuce, Section -B. 2. Evans, DE. 1986 ‘Casiying Pulruded Produc by Glass Loading” st Annual Conference, SP Reinforced Plastics/Compasts insite, Section 6, 3. Loveless, HS. 197, “Mechanical Properties of Pultruded Rod St {33nd Annual Confrence, SPI Reinforced Plastice/Composites Instn, Section 8 4. Glasser, H, I. and J. V. Gnuchel. 1988. “New Approach wo Bulked Rov- ing Upgrades Composite Pecformance” Modern Plastics, 189): 1-120 5. Cameron, NM. 1965. "An vestigation into the Elect of Environmen- {al Treatments on the Strength of E-Glas Fibers” L4A.M. Report No, 714, Universiy of Minos, Urbana, lino. (6. "Thomas, W.F,1960"Aa Investigation othe Factor Likely o Aft the Strength and Propenies of Glass Fibers Physics and Chemistry of Glasses, 10): 4-th 7, Elhans, R. A. 1969. “Characterization of Graphite Fiber/Resin Matix Components” Composite Materials, ASTM STP 460. BIOGRAPHIES ‘Michael W. Klett Michael W. Klet is a Senior Research Chemist at the PPG Fiber Glass Research Center in Pitsburgh, PA. He received his BS. Session 4-E/2‘degree in Chemistry from California University of Pennsylvania in 1979 and his Ph.D. degree in Physical Organic Chemistry at Iowa State University in 1985, Dr. Klett joined PPG in 1986 as a Research Chemist. He has ‘worked in a variety of areas in fiberglass product development for IP applications and is currendy project leader for the pultrusion and flament winding projects. He is a member of the American ‘Chemical Society. TABLE 1. Resin Formulat Components __ DION 810)" ASP 00°" ZELEC UF PERCADOK 16° Benzoyl Peroxide t-Buty! Perbenzoate Styrene Viseésity (cps) SPI Gel Time’ (ain.) SPI Cure Tine (min. Exotherm ("F) * Reichhold Chemical Co. * Engethard Corp. * DuPont. de Nemours & Co. * AKZO Chemicals Co. Baward A. Martine Edvard Martine received his BS. and M.S degrees in Mechanical Engineering from Rensselaer Polytechnic Institute in 1985 and 1988. He is currently a Research Engincer in the Process and Engineering Group at the PPG Fiber Glass Research Center His work includes the development and characterization of fiber ‘lass reinforced structural composites. tion and Physical Properties. Parts By Weicht 10,000 2,400 100 ) TABLE 2. ASTM Test Methods. In-Plane Shear Strength Short. Bean Shear Flexural Tensile Strand Tensile Barco! Hardness TABLE 3. Mechenicel and Method No. 0-3846 2344 0-730) 0-3039 0-2343 2583 Physicol Property Summary. carseat Sa a a mr Sort Geen Start 6.58 -7.59G.M 7.58 6.59 687 74D 5.878) 66S SS TH Sos 7 Feral 6c" 1S ASM ASG Freres (gest 1870 memset testee aware a Fenrey 40s? 18) SSS Feary (48a}® " ns composite Tense? ea 18 oa mom me ontnt () SHOE AT HT HBS HH MR Me mo rel Mertens SS SS SOE OT OS OS 3 ES A wT a 03 em 19 sem ‘saerape vate (at) 3/ Session 4-6.TABLE 4, Physical Property Comparisons F 200 Tensile x Strength Elongation 180 —toterial Sg Sg DION 8101 1.6 a 3 fesin Mix 4a 07 0 moro. 2036 10 46 5 veo Esclass (pristine) 00 _ ‘ + Ashland Chemica) Co. #10, + arco Hardens oes teen ao FIGURE 2, Efect of cure on flexural strength g Ese 200 rt : he § veol- . at ' + A+ + th ; eat ee fe s@F 2 08 So pt : ; Ce ef ob e 3 00 puoP aT ‘ 3 1 1s0, fo vzoh ° oo aes aso are ato asso ‘lee Fument Svaogh a) § 100 L L 1 Stand Tense (lexi) + Stand Tent) 1 800 380 700 “80 {4 Conpoae Suengih 0 Gass Fanon Sength lege Flameot Srengh (ks) FIGURE 1. Corelaion between tense dato ond gloss foment Ores ant waar strength FIGURE 4. Effect of glass filament strength on flexural strength. gi z” F 200 ' 180 5 : i poe f : 140 K f 20h 8s co 7 76 OK arco Hercnass # too! + + + + + CD mPiane Shear 4 Short Beam Shaar Span (in) FIGURE 2, Etec of cure on sheorstengh, Feo A epi FIGURE 5. Effect of span on flexucal stengih Sisson 4E 14