Glass FibersFrederick T. Wallenberger, James C. Watson, and Hong Li, PPG Industries, Inc. GLASS FIBERS are among the most versatile highlighted wherever appropriate but not dis- sion of compositions, melt properties, ﬁber prop-industrial materials known today. They are read- cussed in full. Additional details about ﬁber erties (Ref 12), methods of manufacture, and sig-ily produced from raw materials, which are forming are provided in the section “Glass Melt- niﬁcant product types. An in-depth discussion ofavailable in virtually unlimited supply (Ref 1). ing and Fiber Forming” in this article. composite applications can be found in other ar-All glass ﬁbers described in this article are de- Sizes and Binders. Glass ﬁlaments are highly ticles in this Volume.rived from compositions containing silica. They abrasive to each other (Ref 4). ’Size’ coatings or Glass ﬁbers and fabrics are used in ever in-exhibit useful bulk properties such as hardness, binders are therefore applied before the strand is creasing varieties for a wide range of applica-transparency, resistance to chemical attack, sta- gathered to minimize degradation of ﬁlament tions (Ref 13). A data book is available (Ref 14)bility, and inertness, as well as desirable ﬁber strength that would otherwise be caused by ﬁl- that covers all commercially available E-glass ﬁ-properties such as strength, ﬂexibility, and stiff- ament-to-ﬁlament abrasion. Binders provide lu- bers, whether employed for reinforcement, ﬁltra-ness (Ref 2). Glass ﬁbers are used in the manu- brication, protection, and/or coupling. The size tion, insulation, or other applications. It lists allfacture of structural composites, printed circuit may be temporary, as in the form of a starch-oil manufacturers, their sales ofﬁces, agents, subsid-boards and a wide range of special-purpose prod- emulsion that is subsequently removed by heat- iaries, and afﬁliates, complete with addresses,ucts (Ref 3). ing and replaced with a glass-to-resin coupling and telephone and fax numbers. And it tabulates Fiber Forming Processes. Glass melts are agent known as a ﬁnish. On the other hand, the key properties and relevant supply details of allmade by fusing (co-melting) silica with miner- size may be a compatible treatment that performs E-glass ﬁber grades, that are available in theals, which contain the oxides needed to form a several necessary functions during the subse- market today.given composition. The molten mass is rapidly quent forming operation and which, during im- Special-Purpose Glass Fibers. S-glass, D-cooled to prevent crystallization and formed into pregnation, acts as a coupling agent to the resin glass, A-glass, ECR-glass, ultrapure silica ﬁbers,glass ﬁbers by a process also known as ﬁberi- being reinforced. hollow ﬁbers, and trilobal ﬁbers are special-pur-zation. pose glass ﬁbers. Selected special-purpose glass Nearly all continuous glass ﬁbers are made by ﬁbers are discussed in the subsequent section ofa direct draw process and formed by extruding Glass Fiber Types this article. That section reviews compositions,molten glass through a platinum alloy bushing manufacture, properties, and applications to anthat may contain up to several thousand individ- extent commensurate with their commercial use Glass ﬁbers fall into two categories, low-costual oriﬁces, each being 0.793 to 3.175 mm (Ref 15). general-purpose ﬁbers and premium special-pur-(0.0312 to 0.125 in.) in diameter (Ref 1). While A companion data book (Ref 16) is available pose ﬁbers. Over 90% of all glass ﬁbers are gen-still highly viscous, the resulting ﬁbers are rap- that covers all commercially available high- eral-purpose products. These ﬁbers are knownidly drawn to a ﬁne diameter and solidify. Typ- strength glass ﬁbers including S-glass and, all by the designation E-glass and are subject toical ﬁber diameters range from 3 to 20 lm (118 silica or quartz glass ﬁbers, including Astro- ASTM speciﬁcations (Ref 5). The remainingto 787 lin.). Individual ﬁlaments are combined quartz and Quartzel. It also lists a wide range of glass ﬁbers are premium special-purpose prod-into multiﬁlament strands, which are pulled by woven fabrics, that are commercially available ucts. Many, like E-glass, have letter designationsmechanical winders at velocities of up to 61 m/ in the market of today, ranging from S-glass/ar- implying special properties (Ref 6). Some haves (200 ft/s) and wound onto tubes or forming amid, S-glass/carbon, silica/aramid, and silica/ tradenames, but not all are subject to ASTMpackages. This is the only process that is de- carbon yarns to silica/boron yarns. In addition, speciﬁcations. Speciﬁcally:scribed in detail subsequently in the present ar- it covers all commercially available carbon, ce-ticle. ramic, boron, and high-temperature polymer ﬁ- The marble melt process can be used to form Letter designation Property or characteristic bers and yarns. This data book also lists all yarnspecial-purpose, for example, high-strength ﬁ- E, electrical Low electrical conductivity counts, fabric constructions, fabric weights, andbers. In this process, the raw materials are S, strength High strength commercial sources. C, chemical High chemical durabilitymelted, and solid glass marbles, usually 2 to 3 M, modulus High stiffness ASTM Test Methods. ASTM has publishedcm (0.8 to 1.2 in.) in diameter, are formed from A, alkali High alkali or soda lime glass standard test methods for glass density (Ref 17),the melt. The marbles are remelted (at the same D, dielectric Low dielectric constant alternating current loss characteristics and di-or at a different location) and formed into glass electric constant (Ref 18), direct current conduc-ﬁbers. Glass ﬁbers can also be down drawn from tance of insulating materials (Ref 19), dielectricthe surface of solid preforms. Although this is Table 1 gives compositions and Table 2 gives breakdown voltage and dielectric strength (Refthe only process used for manufacturing optical physical and mechanical properties of commer- 20), softening point of glass (Ref 21), annealingﬁbers, which are not discussed in this Volume, it cial glass ﬁbers. point and strain point of glass by ﬁber elongationis a specialty process for manufacturing struc- General-purpose glass ﬁbers (E-glass vari- (Ref 22), annealing point and strain point oftural glass ﬁbers such as silica or quartz glass ants) are discussed in the following section of glass by beam bending (Ref 23), viscosity (Refﬁbers. These and other specialty processes are this article, which provides an in-depth discus- 24), liquidus temperature (Ref 25), and coefﬁ-
2 / Constituent MaterialsTable 1 Compositions of commercial glass ﬁbers Composition, wt%Fiber Ref SiO2 B2O3 Al2O3 CaO MgO ZnO TiO2 Zr2O3 Na2O K2O Li2O Fe2O3 F2General-purpose ﬁbersBoron-containing E-glass 1, 2 52–56 4–6 12–15 21–23 0.4–4 ... 0.2–0.5 ... 0–1 Trace ... 0.2–0.4 0.2–0.7Boron-free E-glass 7 59.0 ... 12.1 22.6 3.4 ... 1.5 ... 0.9 ... ... 0.2 ... 8 60.1 ... 13.2 22.1 3.0 ... 0.5 ... 0.6 0.2 ... 0.2 0.1Special-purpose ﬁbersECR-glass 1, 2 58.2 ... 11.6 21.7 2.0 2.9 2.5 ... 1.0 0.2 ... 0.1 TraceD-glass 1, 2 74.5 22.0 0.3 0.5 ... ... ... ... 1.0 Ͻ1.3 ... ... ... 2 55.7 26.5 13.7 2.8 1.0 ... ... ... 0.1 0.1 0.1 ... ...S-, R-, and Te-glass 1, 2 60–65.5 ... 23–25 0–9 6–11 ... ... 0–1 0–0.1 ... ... 0–0.1 ...Silica/quartz 1, 2 99.9999 ... ... ... ... ... ... ... ... ... ... ... ...cient of linear thermal expansion of plastics (Ref to eliminate boron from the off-gases of boron- ASTM standards for E-glass (Ref 5) cover all26). containing melts. Alternatively, the use of envi- three commercial E-glass variants, distinguish- Some ﬁber properties (Ref 4), such as tensile ronmentally friendly boron-free E-glass is re- ing E-glasses by end use. Compositions contain-strength, modulus, and chemical durability, are quired. These melts do not contain, and therefore ing 5 to 10 wt% by weight of boron oxide aremeasured on the ﬁbers directly. Other proper- do not emit, boron into the environment during certiﬁed for printed circuit board and aerospaceties, such as relative permittivity, dissipation processing. As a result, a boron-free E-glass applications. Compositions containing 0 to 10factor, dielectric strength, volume/surface resis- product was recently introduced into the market wt% by weight of boron oxide are certiﬁed fortivities, and thermal expansion, are measured on by Fiberglas (Owens Corning Corp., Toledo, general applications. According to these stan-glass that has been formed into a bulk patty or OH) under the trademark Advantex. dards, E-glass compositions for either type of ap-block sample and annealed (heat treated) to re- Commercial boron-containing E-glass comes plication may also contain 0 to 2 wt% alkali ox-lieve forming stresses. Properties such as den- in two variants. One commercial variant is de- ide and 0 to 1 wt% ﬂuoride. The more recentsity and refractive index are measured on both rived from the quaternary SiO2-Al2O3-CaO- boron-free E-glass variants may also be ﬂuorine-ﬁbers and bulk samples, in annealed or unan- MgO (Ref 2, 4, 6, 27), and the other is derived free.nealed form. from the ternary Oxide Compositions. E-glasses of any type SiO2-Al2O3-CaO phase diagram (Ref 2, 4, 6, are general-purpose ﬁbers because they offer 28). Commercial E-glasses in the ternary SiO2- useful strength at low cost. Table 1 presents theGeneral-Purpose Glass Fibers Al2O3-CaO system contain a small amount oxide components and their ranges for the two (Ͻ0.6 wt%) of MgO that is not deliberately types of E-glass ﬁbers that are currently being Types. Two generic types of E-glass (Ref 6) added but obtained as by-product (or tramp) produced and used in composites. A range isare known in the market today. The incumbent from other ingredients. On the other hand, com- given for each with regard to its oxide compo-E-glass contains 5 to 6 wt% of boron oxide. mercially available boron-free E-glass is derived nents because each manufacturer, and even dif-Stringent environmental regulations require the from the quaternary SiO2-Al2O3-CaO-MgO ferent manufacturing plants of the same com-addition of costly emission abatement systems phase diagram (Ref 2, 7, 8, 29). pany, may use slightly different compositions forTable 2 Physical and mechanical properties of commercial glass ﬁbers Annealing Straining Log 3 forming temperature(a) Liquidus temperature Softening temperature temperature temperature Bulk density,Fiber ЊC ЊF ЊC ЊF ЊC ЊF ЊC ЊF ЊC ЊF annealed glass, g/cm3General-purpose ﬁbersBoron-containing E-glass 1160–1196 2120–2185 1065–1077 1950–1970 830–860 1525–1580 657 1215 616 1140 2.54–2.55Boron-free E-glass 1260 2300 1200 2190 916 1680 736 1355 691 1275 2.62Special-purpose ﬁbersECR-glass 1213 2215 1159 2120 880 1615 728 1342 691 1275 2.66–2.68D-glass ... ... ... ... 770 1420 ... ... 475 885 2.16S-glass 1565 2850 1500 2730 1056 1935 ... ... 760 1400 2.48–2.49Silica/quartz Ͼ2300 Ͼ4170 1670 3038 ... ... ... ... ... ... 2.15 Dielectric Volume Coefﬁcient constant resistivity Weight of linear Speciﬁc at room Dielectric at room Refractive loss in 24 h Tensile strength Filament expansion, heat, temperature strength, temperature index in 10% at 23 ЊC (73 ЊF) Young’s modulus elongationFiber 10–6/ЊC cal/g/ЊC and 1 MHz kV/cm log10 (X cm) (bulk) H2SO4, % MPa ksi GPa 6 10 psi at break, %General-purpose ﬁbersBoron-containing E-glass 4.9–6.0 0.192 5.86–6.6 103 22.7–28.6 1.547 ϳ41 3100–3800 450–551 76–78 11.0–11.3 4.5–4.9Boron-free E-glass 6.0 ... 7.0 102 28.1 1.560 ϳ6 3100–3800 450–551 80–81 11.6–11.7 4.6Special-purpose ﬁbersECR-glass 5.9 ... ... ... ... 1.576 5 3100–3800 450–551 80–81 11.6–11.7 4.5–4.9D-glass 3.1 0.175 3.56–3.62 ... ... 1.47 ... 2410 349 ... ... ...S-glass 2.9 0.176 4.53–4.6 130 ... 1.523 ... 4380–4590 635–666 88–91 12.8–13.2 5.4–5.8Silica/quartz 0.54 ... 3.78 ... ... 1.4585 ... 3400 493 69 10.0 5(a) The log 3 forming temperature is the temperature of a melt at a reference viscosity of 100 Pa • s (1000 P). Source: Ref 2, 7–10, 11
Glass Fibers / 3the same glass. These variations result mainly and boron-containing E-glasses. Elastic modulus acid resistance and short-term alkali resistancefrom differences in the available glass batch (raw (or ﬁber stiffness) of boron-free E-glasses is (Ref 27).materials). Tight control is maintained within a about 5% higher than that of boron-containing The addition of high levels of ZnO and TiO2given production facility to optimize composi- E-glasses, while pristine, virgin, or single-ﬁla- to the boron-free quaternary E-glass system fur-tional consistency and maximize production ef- ment tensile strength is said to be about the same ther enhances the corrosion resistance of the re-ﬁciencies. for both types of E-glasses when both are tested sulting ECR glass ﬁbers while at the same time As shown in Table 1, commercial, boron-con- at room temperature (Ref 8, 9). reducing the log 3 forming temperature. Thetaining E-glass compositions (Ref 1, 2, 4, 6, 12, Physical Properties. In addition, Table 2 product and process advantage are obtained at a24) differ substantially from boron-free E-glass compares the physical properties of the boron- cost penalty. About 2% ZnO and two additionalcompositions. The silica content for commercial free and boron-containing E-glasses. Most im- percent TiO2 are required, and both materials areboron-containing E-glasses ranges from 52 to 56 portantly, the corrosion resistance of boron-free known to be costly batch ingredients.wt% by weight, and for commercial boron-free E-glasses was found to be seven times higher S-Glass, R-Glass, and Te-Glass. The tensileE-glasses from 59 to 61 wt%. The alumina con- than that of boron-containing E-glasses when strength of glass ﬁbers is determined by thetent generally ranges from 12 to 15 wt% for these tested at room temperature for 24 h in 10% sul- structure connectivity of the silicate network, no-boron-containing E-glasses and from 12 to 13.5 furic acid. It approaches that of ECR glass ﬁbers tably, by the absence of alkali oxides, which arewt% for these boron-free E-glasses. The calcia (Ref 9, 10). not readily integrated into the structure. Thecontent ranges from 21 to 23 wt% for these com- Boron-free E-glasses have a slightly higher structure of boron oxide, though being a part ofmercial boron-containing E-glasses and from 22 density (2.62 g/cm3) than boron-containing E- the network, is weaker than that of silicon oxide,to 23 wt% for these boron-free E-glasses. glasses (2.55 g/cm3), but the density of both ﬁ- and therefore, boron oxide serves as a ﬂux. Sev- For commercial, boron-containing, ternary or bers is lower than that of ECR glass (2.66 to 2.68 eral high-strength glass ﬁbers are known, includ-quaternary E-glasses, the magnesia content g/cm3), a corrosion-resistant special-purpose ﬁ- ing S-glass, Te-glass, and R-glass (Ref 2). Allranges from 0.4 wt% (tramp only) to greater ber. Boron-free E-glasses have a higher refrac- offer 10 to 15% higher strength than E-glass atamounts if magnesia (dolomite) is deliberately tive index and linear expansion coefﬁcient than room temperature, but their real value is theiradded. For commercial boron-free E-glasses, it boron-containing E-glass ﬁbers. The refractive ability to withstand higher in-use temperaturesranges from 3.1 to 3.4 wt% (see Table 1). The index of both E-glasses is lower than that of ECR than E-glass. These ﬁbers are used in militaryboron oxide content ranges from 5 to 6% for glass. The linear expansion coefﬁcient of ECR applications. Stringent quality-control proce-commercial boron-containing E-glasses, and it is glass ﬁbers is midway between that of the two dures are necessary to meet military speciﬁca-zero for boron-free E-glasses. The titania content E-glasses. tions.ranges from 0.4 to 0.6 wt% for commercial bo- Boron-free E-glasses have a slightly higher di- S-glass and Te-glass are derivatives of the ter-ron-containing E-glasses. For boron-free E- electric constant (7.0) than boron-containing E- nary SiO2-Al2O3-CaO system. R-glass is a de-glasses, it ranges from 0.5 wt% (Ref 8) to 1.5 glasses (5.9 to 6.6) when measured at room tem- rivative of the quaternary SiO2-Al2O3-CaO-wt% (Ref 7) (see also Table 1). perature and at a frequency of 1 MHz. As a MgO system. S-glass and S-2 glass ﬁbers, a Environmentally friendly E-glass melts are result, boron-containing, but not boron-free, E- product variant, have the same glass compositionboron-free and ﬂuorine-free. However, the log 3 glass ﬁbers are needed for electronic circuit (Ref 2) but different coatings. While internalﬁber forming or ﬁberization temperature (TF) of boards and aerospace applications. On the other structural uniformity (high strength) is achievedboron-free E-glass melts may be as much as 100 hand, boron-free and boron-containing E-glass with these boron-free and alkali-free composi-to 110 ЊC (180 to 200 ЊF) higher than that of ﬁbers are used in structural composites where the tions, their forming temperatures are higher thanboron-containing E-glass melts (Fig. 1). The log dielectric constant is of no concern. Composite that of E-glass. Attainment of high in-use tem-3 forming temperature is the temperature of a and laminate uses of all glass ﬁbers are discussed peratures is a deﬁnite product advantage, butmelt at a reference viscosity of 100 Pa • s (1000 in other articles in this Volume.P). In addition, the softening point of boron-freeE-glass is 60 to 90 ЊC (110 to 160 ЊF) higher also Temperature, °Fthan that of a boron-containing E-glass. The Special-Purpose Glass Fibershigher process temperature requires more pro- 5.5 1800 2000 2200 2400 2600cess energy, but the higher softening point fa- Types. Special-purpose ﬁbers, which are ofcilitates higher use temperatures. commercial signiﬁcance in the market today, in- Melt Properties. According to Table 2, the clude glass ﬁbers with high corrosion resistance 5.0log 3 forming temperature, TF, of boron-contain- (ECR-glass), high strength (S-, R-, and Te-ing E-glasses ranges from 1140 to 1185 ЊC (2085 glass), with low dielectric constants (D-glass), 4.5 Boron-free E-glassto 2165 ЊF). The liquidus temperature (TL) is the high strength ﬁbers, and pure silica or quartz ﬁ-temperature below which solid (crystals) will bers, which can be used at ultrahigh tempera- Viscosity, log poise 4.0form. It ranges form 1050 to 1064 ЊC (1920 to tures. These ﬁbers will be discussed in the fol-1945 ЊF). The difference between forming and lowing paragraphs. Others special-purpose ﬁbers 3.5liquidus temperature (DT) ranges from 81 to 90 include A-glass, C-glass, hollow ﬁbers, bicom-ЊC (146 to 162 ЊF). In contrast, the log 3 ﬁber ponent ﬁbers, and trilobal ﬁbers. These special-forming temperature of boron-free E-glasses purpose glass ﬁbers have recently been reviewed 3.0ranges from 1250 to 1264 ЊC (2280 to 2307 ЊF), in detail (Ref 2).the liquidus temperature from 1146 to 1180 ЊC ECR-Glass. The corrosion resistance of glass 2.5(2095 to 2155 ЊF), and the difference between ﬁbers is determined by their chemical structure.forming and liquidus temperature (DT) from 86 It has already been noted in the preceding sec- 2.0 Boron-containing E-glassto 104 ЊC (155 to 187 ЊF) (Ref 7–10). Finally, tion on general-purpose glass ﬁbers that boron-the softening point of boron-containing E- free E-glass ﬁbers derived from the quaternary 1.5glasses ranges from 830 to 860 ЊC (1525 to 1580 SiO2-Al2O3-CaO-MgO phase diagram have 900 1000 1100 1200 1300 1400 1500ЊF); that of boron-free E-glasses is about 916 ЊC higher acid resistance than E-glass ﬁbers that Temperature, °C(1680 ЊF). are derived from the ternary SiO2-Al2O3-CaO Mechanical Properties. Table 2 also com- phase diagram but have high boron levels. The Fig. 1 Viscosity of boron-free and boron-containing E-pares the mechanical properties of the boron-free ECR glass ﬁbers offer enhanced long-term glass
4 / Constituent Materialshigher melt temperatures, more process energy, high-temperature ﬁbers have lower dielectric glass, ultrapure silica ﬁbers, and D-glass (seeand more costly bushing alloys are required. constants than solid E-glass. They, too, can and Ref 2). Silica/Quartz Fibers. Glass ﬁbers with in- are being used to reinforce printed circuit board Batch Mixing and Melting. The glass melt-creasing SiO2 levels can be used in applications (PCB) laminates. However, silica ﬁbers have a ing process begins with the weighing and blend-requiring increasingly high in-use temperatures. low modulus and are, therefore, less effective as ing of selected raw materials. In modern ﬁber-High-silica ﬁbers (95% SiO2) are amorphous reinforcing ﬁbers. Hollow ﬁbers, although ini- glass plants, this process is highly automated,glass ﬁbers. They are obtained by acid leaching tially effective because of their low dielectric with computerized weighing units and enclosedof borosilicate E-glass fabrics, which are, in turn, constant, lose their dielectric properties if mois- material transport systems. The individual com-used as insulation blankets at temperatures up to ture can seep into the laminate structure. ponents are weighed and delivered to a blending1040 ЊC (1900 ЊF). Pure silica ﬁbers (99% SiO2) station where the batch ingredients are thor-are made by dry spinning from aqueous water- oughly mixed before being transported to theglass solutions. They are known by the traden- Glass Melting and Fiber Forming furnace.ame “Silfa” and mostly are used as yarns, for Fiberglass furnaces generally are divided intoexample, for wire insulation at temperatures up A glass is an amorphous solid obtained by three distinct sections (Fig. 2). Batch is deliveredto 1090 ЊC (1990 ЊF). For details see Ref 2. They cooling a melt (i.e., liquid phase) sufﬁciently fast into the furnace section for melting, removal ofare not used in composite applications and are that crystallization (devitriﬁcation) cannot occur. gaseous inclusions, and homogenization. Then,therefore not shown in Table 2. When the melt is cooled slowly, crystallization the molten glass ﬂows into the reﬁner section, Ultrapure silica glass ﬁbers or quartz ﬁbers can occur at the liquidus temperature, TL, where where the temperature of the glass is lowered(99.99% SiO2), which are down-drawn from pre- crystals and melt are in equilibrium, or below. from 1370 ЊC (2500 ЊF) to about 1260 ЊC (2300forms (Ref 2) in a containerless process, are also Glass ﬁbers are therefore obtained at high cool- ЊF). The molten glass next goes to the forehearthamorphous, despite the fact that the trivial name ing rates. Chemically, a glass consists of a silica section located directly above the ﬁber-forming“quartz” or trade names Quartzel and Astro- network. Other oxides facilitate melting, homog- stations. The temperatures throughout this pro-quartz would imply the presence of the hexag- enizing, removal of gaseous inclusions, and ﬁber cess are prescribed by the viscosity characteris-onal crystal structure of quartz. Ultrapure silica formation at optimum temperatures. This section tics of the particular glass. In addition, the physi-(quartz) ﬁbers combine superior high-tempera- addresses the generic glass-melting and ﬁber- cal layout of the furnace can vary widely,ture resistance with superior transparency to ul- forming process, including the viscosity versus depending on the space constraints of the plant.traviolet (UV) and longer wavelength radiation. temperature proﬁle that is required for general- Fiberizing and Sizing. The conversion ofFor example, in a composite radome on the nose purpose E-glass glass ﬁbers and, more speciﬁ- molten glass in the forehearth into continuousof an aircraft, they protect delicate radar equip- cally, for E-glass ﬁbers containing 5 to 6% boron glass ﬁbers is basically an attenuation processment from ﬂying objects, lightning and static oxide (see Ref 1 for details). (Fig. 3). The molten glass ﬂows through a plat-discharge (Ref 30). The purest of all commercial Depending on ﬁber diameter, optimum ﬁber inum-rhodium alloy bushing with a large num-silica glass or quartz ﬁbers (99.999% SiO2) are formation is achieved with melts having a vis- ber of holes or tips (400 to 8000, in typical pro-obtained by dry-spinning of a reagent grade te- cosity ranging from log 2.5 to log 3 P. The ge- duction). The bushing is heated electrically, andtraethylorthosilicate sol-gel (Ref 2). neric melting and forming process that is re- the heat is controlled very precisely to maintain All ultrapure silica glass or quartz ﬁbers are quired for boron-free E-glass is the same as that a constant glass viscosity. The ﬁbers are drawnused in yarn and in composite applications and required for boron-containing E-glass, but the down and cooled rapidly as they exit the bush-are, therefore, shown in Table 2. Ultrapure and viscosity/temperature proﬁle differs. The relative ing.pure silica yarns and fabrics can be used at tem- forming temperatures can be deduced from the A sizing is then applied to the surface of theperatures up to 1090 ЊC (1990 ЊF), high silica Fulcher curves shown in Fig. 1. They will be ﬁbers by passing them over an applicator thatfabrics at up to 1040 ЊC (1900 ЊF), and S-glass, proportionately higher for boron-free E-glass at continually rotates through the sizing bath toTe-glass, and R-glass yarns and fabrics at up to equal melt viscosities between log 2.5 to log 3.0 maintain a thin ﬁlm through which the glass ﬁl-815 ЊC (1500 ЊF) (for process and product details P. This section does not address the glass melting aments pass. It is this step, in addition to thesee Ref 2). and ﬁber forming processes required for the spe- original glass composition, which primarily dif- D-Glass. The electrical properties of glass ﬁ- cial-purpose glass ﬁbers, that is, ECR-glass, S- ferentiates one ﬁberglass product from another.bers are determined by their volume resistivity,surface conductivity, dielectric constant and losstangent (Ref 2). E-glass with its relatively highdielectric constant is the major reinforcing ﬁberfor printed circuit board (PCB) laminates in themarket today, but miniaturization drives the in-dustry toward specialty ﬁbers with lower dielec-tric constants and lower dielectric loss tangents. Several low D-glass variants are known. Allhave very high B2O3 levels (20 to 26%) and,therefore, much lower dielectric constants thanE-glass (4.10 to 3.56 versus 6.86 to 7.00). ThoseD-glass variants having low dielectric loss tan-gents as well (Ref 8) are said to offer the highestvalue in-use when used to reinforce PCB lami-nates. Because of their high cost, however, anyD-glass version will remain a low volume spe-cialty ﬁber. The very high boron-oxide levels,which are needed and in part emitted from themelt, may require an entirely different specialtyprocess (see Ref 2 for details). For very different reasons, ultrapure silica ﬁ-bers, hollow E-glass ﬁbers, S-glass, and other Fig. 2 Furnace for glass melting
Glass Fibers / 5The components of the sizing impart strand in- trolled by the take-up device. Fiber diameter is speciﬁc fabrication area for conversion into thetegrity, lubricity, resin compatibility, and adhe- also affected by bushing temperature, glass vis- ﬁnished ﬁberglass roving, mat, chopped strand,sion properties to the ﬁnal product, thus tailoring cosity, and the pressure head over the bushing. or other product.the ﬁber properties to the speciﬁc end-use re- The most widely used take-up device is the In recent years, processes have been devel-quirements. After applying the sizing, the ﬁla- forming winder, which employs a rotating collet oped to produce ﬁnished roving or choppedments are gathered into a strand before ap- and a traverse mechanism to distribute the strand products directly during forming, thus leading toproaching the take-up device. If small bundles in a random manner as the forming package the term direct draw roving or direct choppedof ﬁlaments (split strands) are needed, multiple grows in diameter. This facilitates strand re- strand. Special winders and choppers designedgathering devices (often called shoes) are used. moval from the package in subsequent process- to perform in the wet-forming environment are Fiber Diameters. The attenuation rate, and ing steps, such as roving or chopping. The form- used in these cases (Fig. 4).therefore the ﬁnal ﬁlament diameter, is con- ing packages are dried and transferred to the Yarn Nomenclature. It is standard practice in the ﬁberglass industry to refer to a speciﬁc ﬁlament diameter by a speciﬁc alphabet desig- nation, as listed in Table 3. Fine ﬁbers, which are used in textile applications, range from D through G. One reason for using ﬁne ﬁbers is to provide enough ﬂexibility to the yarn to enable it to be processed in high-speed twisting and weaving operations. Conventional plastics rein- forcement, however, uses ﬁlament diameters that range from G to T. Important Commercial Products Once the continuous glass ﬁbers have been produced they must be converted into a suitable product form for their intended composite ap- plication. The major ﬁnished forms for E-glass ﬁbers are continuous roving, woven roving, ﬁ- berglass mat, chopped strand, and yarns for tex- tile applications. Fiberglass roving is produced by collecting a bundle of strands into a single large strand, which is wound into a stable, cylindrical pack- age. This is called a multiend roving process. The process begins by placing a number of oven- dried forming packages into a creel. The ends are then gathered together under tension and col- lected on a precision roving winder that has a constant traverse-to-winding ratio, and is calledFig. 3 Fiberglass forming process the waywind. This ratio has a signiﬁcant effect on package stability, strand characteristics, and ease of payout in subsequent operations. The yield (meter per kilogram, or yard per pound) of the ﬁnished roving is determined by the number of input ends and the yield of the input strand or sliver. Final package weight and dimensions can be made to vary widely, depending upon the re- quired end-use. Figure 4 shows the entire pro- cess. Rovings are used in many applications. When used in a spray-up fabrication process, the roving is chopped with an air-powered gun that propels the chopped-glass strands to a mold while si- multaneously applying resin and catalyst in the compact ratio. This process is commonly used for bath tubs, shower stalls, and many marine applications. In another important process, the production of sheet molding compound (SMC), the roving is chopped onto a bed of formulated polyester resin and compacted into a sheet, which thickens with time. This sheet is then placed in a press and molded into parts. Many ﬁber-reinforced plastic (FRP) automotive bodyFig. 4 Multiend roving process production panels are made by this process.
6 / Constituent Materials Filament winding and pultrusion are processes from low to high, depending on the application. area where they are dried, screened, and pack-that use single-end rovings in continuous form. For example, hand lay-up processes used to aged. The direct-chop process has provided theApplications include pipes, tanks, leaf springs, moderate corrosion-resistant liners or boat hulls industry with a wide variety of chopped rein-and many other structural composites. In these require high solubility, whereas closed-mold forcements for compounding with resins.processes the roving is passed through a liquid processes such as cold press or compression Chopped glass is widely used as a reinforce-resin bath and then shaped into a part by winding molding require low solubility to prevent wash- ment in the injection molding industry. The glassthe resin-impregnated roving onto a mandrel or ing in the mold during curing. and resin may be dry blended or extrusion com-by pulling it through a heated die. Because of a Continuous-strand mat is formed in a similar pounded in a preliminary step before molding,property called catenary (the presence of some manner but without chopping, and, usually, less or the glass may be fed directly into the moldingstrands that have a tendency to sag within a bun- binder is required because of increased mechan- machine with the plastic resin. Hundreds of dif-dle of strands), multiend rovings sometimes do ical entanglement, which provides some inherent ferent parts for many applications are made innot process efﬁciently. Catenary is caused by un- integrity. Continuous-strand mat may be used in this manner. Chopped glass may also be used aseven tension in the roving process that results in closed mold processes and as a supplemental a reinforcement in some thermosetting applica-poor strand integrity. product in unidirectional processes such as pul- tions, such as bulk molding compounds. While providing desirable entanglement for trusion, where some transverse strength is re- Milled ﬁbers are prepared by hammer millingtransverse strength in pultrusion, the looser ends quired. A number of specialty mats are also pro- chopped or sawed continuous strand glass ﬁbers,in the roving may eventually cause loops and duced. Surfacing veil made with C-glass is used followed by chemically sizing for some speciﬁcbreakouts in close-tolerance oriﬁces, making re- to make corrosion-resistant liners for pipes and applications and by screening to length. Fiberinforced plastics processing difﬁcult. Conse- tanks. Surfacing veils made from other glass lengths typically vary from particulates to screenquently, the process of direct forming single-end compositions are used to provide a smooth ﬁn- opening dimensions for the reported nominal 1 1rovings was developed by using very large bush- ished surface in some applications. Glass tissue length (0.79 to 6.4 mm, or 32 to 4 in.). Asings and a precision winder specially designed is used in some vinyl ﬂooring products. such, milled ﬁbers have a relatively low aspectto operate in the severe forming environment. Combinations of a mat and woven roving ratio (length to diameter). They provide someNo subsequent step other than drying is required. have been developed for speciﬁc products in re- increased stiffness and dimensional stability toSingle-end rovings have become the preferred cent years. In many lay-up processes the lami- plastics but minimal strength. Their use is pri-product for many ﬁlament-winding and pultru- nate is constructed from alternate layers of ﬁ- marily in phenolics, reaction-injection moldedsion applications. berglass mat and woven roving. Fiberglass urethanes, ﬂuorocarbons, and potting com- Woven roving is produced by weaving ﬁber- producers thus began to provide products that pounds.glass rovings into a fabric form. This yields a make this process more efﬁcient. The appropri- Fiberglass paper is the reinforcing elementcoarse product that is used in many hand lay-up ate weights of ﬁberglass mat (usually chopped- for ﬁberglass rooﬁng shingles. Chopped strandsand panel molding processes to produce FRPs. strand mat) and woven roving are either bound of 25 to 50 mm (1 to 2 in.) length are usuallyMany weave conﬁgurations are available, de- together with a chemical binder or mechanically used in making ﬁberglass paper or a thin ﬁber-pending on the requirements of the laminate. knit or stitched together. This product can then glass mat. In this process, chopped ﬁbers are dis-Plain or twill weaves provide strength in both be used as a signiﬁcant labor saver by the fab- persed in water to form a dilute solution. Thedirections, while a unidirectionally stitched or ricators. ﬁberglass strands ﬁlamentize during the mixingknitted fabric provides strength primarily in one Chopped strand products are produced by and dispersion process. The solution is pumpeddimension. Many novel fabrics are currently two major processes. In the ﬁrst process, dried onto a continuously moving chain, where mostavailable, including biaxial, double-bias, and tri- forming packages are used as a glass source. A of the water is removed by vacuum, leaving be-axial weaves for special applications. number of strand ends are fed into a chopper, hind a uniformly distributed, thin ﬁberglass mat. Fiberglass mats may be produced as either which chops them into the correct length, typi- A binding resin is added on-line, followed by 1 1continuous- or chopped-strand mats. A chopped- cally 3.2 to 12.7 mm ( 8 to 2 in.). The product drying and curing, to form the ﬁberglass paper.strand mat is formed by randomly depositing is then screened to remove fuzz and contami- This paper is then combined with the appropriatechopped ﬁbers onto a belt or chain and binding nation and boxed for shipment (Fig. 5). The sec- resin system to form rooﬁng shingles.them with a chemical binder, usually a thermo- ond process, used in recent years to produce Textile yarns are ﬁne-ﬁber strands of yarnplastic resin with a styrene solubility ranging many chopped-strand products, is the direct- from the forming operation that are air dried on chop process. In this process, large bushings are the forming tubes to provide sufﬁcient integrityTable 3 Filament diameter nomenclature used in forming, and the strands are chopped in to undergo a twisting operation. Twist provides a wet state directly after sizing is applied. The additional integrity to yarn before it is subjected Filament diameter wet, chopped strands are then transported to an to the weaving process, a typical twist consistingAlphabet lm 10–4 in.AA 0.8–1.2 0.3–0.5A 1.2–2.5 0.5–1.0B 2.5–3.8 1.0–1.5C 3.8–5.0 1.5–2.0D 5.0–6.4 2.0–2.5E 6.4–7.6 2.5–3.0F 7.6–9.0 3.0–3.5G 9.0–10.2 3.5–4.0H 10.2–11.4 4.0–4.5J 11.4–12.7 4.5–5.0K 12.7–14.0 5.0–5.5L 14.0–15.2 5.5–6.0M 15.2–16.5 6.0–6.5N 16.5–17.8 6.5–7.0P 17.8–19.0 7.0–7.5Q 19.0–20.3 7.5–8.0R 20.3–21.6 8.0–8.5S 21.6–22.9 8.5–9.0T 22.9–24.1 9.0–9.5U 24.1–25.4 9.5–10 Fig. 5 Chopped-strand production
Glass Fibers / 7of up to one turn per inch. The twisting operation ● The ﬁrst letter speciﬁes the glass composi- The product brochures from various weavers asis shown in Fig 6. In many instances, heavier tion, in this case, E-glass. well as to Ref 4 should be consulted for detailsyarns are needed for the weaving operation. This ● The second letter speciﬁes the ﬁlament type on commercially available fabrics. The Glass-is normally accomplished by twisting together (staple, continuous, texturized) (in the case, Fibre Dictionary and Databook (Ref 14) shouldtwo or more single strands, followed by a plying of ECG 75 2/4, continuous). be consulted for even greater detail and/or for aoperation. Plying essentially involves retwisting ● The third letter speciﬁes the ﬁlament diameter summary of all commercially available yarns.the twisted strands in the opposite direction from (in this case, G). Fiberglass Fabric. Fiberglass yarns are con-the original twist. The two types of twist nor- ● The next series of numbers represents the ba- verted to fabric form by conventional weaving 1mally used are known as S and Z, which indicate sic strand yield in terms of 100 th of the operations. Looms of various kinds are used inthe direction in which the twisting is done. Usu- yield (in this case, 75 means 7500 yd/lb). the industry, but the air jet loom is the most pop-ally, two or more strands twisted together with ● The fraction represents the number of strands ular. The major characteristics of a fabric includean S twist are plied with a Z twist in order to twisted together (numerator) to form a single its style or weave pattern, fabric count, and thegive a balanced yarn. Thus, the yarn properties, end and the number of such ends plied to- construction of warp yarn and ﬁll yarn. Together,such as strength, bundle diameter, and yield, can gether (denominator) to form the ﬁnal yarn. these characteristics determine fabric propertiesbe manipulated by the twisting and plying opera- In the above case, 2/4 means two basic such as drapability and performance in the ﬁnaltions. strands are twisted together to form a single composite. The fabric count identiﬁes the num- The yarn nomenclature for ﬁberglass yarns end, and four such ends are plied together ber of warp and ﬁll yarns per inch. Warp yarnsconsists of both letters of the alphabet and num- (usually in the opposite direction) to form the run parallel to the machine direction, and ﬁllbers. For instance, in ECG 75 2/4: ﬁnal yarn. yarns are perpendicular. There are basically four weave patterns: plain, basket, twill, and satin. Plain weave is the sim- plest form, in which one warp yarn interlaces over and under one ﬁll yarn. Basket weave has two or more warp yarns interlacing over and un- der two or more ﬁll yarns. Twill weave has one or more warp yarns ﬂoating over at least two ﬁll yarns. Satin weave (crowfoot) consists of one warp yarn interfacing over three and under one ﬁll yarn to give an irregular pattern in the fabric. The eight-harness satin weave is a special case, in which one warp yarn interlaces over seven and under one ﬁll yarn to give an irregular pattern. In fabricating a composite part, the satin weave gives the best conformity to complex contours, followed in descending order by twill, basket, and plain weaves. Texturized Yarn. Texturizing is a process in which the textile yarn is subjected to an air jet that impinges on its surface to make the yarn ’ﬂuffy’’ (Fig. 7). The air jet causes the surface ﬁlaments to break at random, giving the yarn a bulkier appearance. The extent to which this oc- curs can be controlled by the velocity of the air jet and the yarn feed rate. The texturzing processFig. 6 Twisting allows the resin-to-glass ratio to be increased in the ﬁnal composite. One of the major applica- tions of texturized yarns is as an asbestos re- placement. Carded Glass Fibers. Carding is a process that makes a staple ﬁberglass yarn from contin- uous yarn. The continuous yarn is chopped into 38 to 50 mm (1.5 to 2.0 in.) lengths, and then aligned in one direction in a mat form. It is ﬁ- nally converted to a staple yarn. The yarn pro- duced by this process can absorb much more resin than texturized yarn. Carded glass ﬁbers are also used as an asbestos replacement in friction applications, such as automotive brake linings. REFERENCES 1. K.L. Loewenstein, The Manufacturing Technology of Continuous Glass Fibers, 3rd revised ed., Elsevier, 1993 2. F.T. Wallenberger, Structural Silicate andFig. 7 Texturizing Silica Glass Fibers, in Advanced Inorganic
8 / Constituent Materials Fibers Processes, Structures, Properties, Handbook of Glass Data, Part A, Elsevier, 21. “Standard Test Method for Softening Point Applications, F.T. Wallenberger, Ed., Klu- 1983, p 75 of Glass,” C 338, Annual Book of ASTM wer Academic Publishers, 1999, p 129– 12. P.F. Aubourg and W.W. Wolf, “Glass Fibers- Standards, ASTM 168 Glass Composition Research,” presented at 22. “Standard Test Method for Annealing Point 3. F.T. Wallenberger, Melt Viscosity and Mod- Glass Division Meeting (Grossinger, NY), and Strain Point of Glass by Fiber Elonga- ulus of Bulk Glasses and Fibers: Challenges American Ceramic Society, Oct 1984 tion,” C 336, Annual Book of ASTM Stan- for the Next Decade, in Present State and 13. J.C. Watson and N. Raghupathi, Glass Fi- dards, ASTM Future Prospects of Glass Science and Tech- bers, in Composites, Vol 1, Engineered Ma- 23. “Standard Test Method for Annealing Point nology, Proc. of the Norbert Kreidl Sym- terials Handbook, ASM International, 1987, and Strain Point of Glass by Beam Bend- posium (Triesenberg, Liechtenstein), 1994, p 107–111 ing,” C 598, Annual Book of ASTM Stan- p 63–78 14. T.F. Starr, Glass-Fibre Dictionary and Da- dards, ASTM 4. D.M. Miller, Glass Fibers, Composites, Vol tabook, 2nd ed., Chapman & Hall, 1997 24. “Standard Practice for Measuring Viscosity 1, Engineered Materials Handbook, ASM 15. W.W. Wolf and S.L. Mikesell, Glass Fibers, of Glass Above the Softening Point,” C965, International, 1987, p 45–48 Encyclopedia of Materials Science and En- Annual Book of ASTM Standards, ASTM 5. “Standard Speciﬁcation for Glass Fiber gineering, 1st Edition, 1986 25. “Standard Practices for Measurement of Li- Strands”, D 578-98, Annual Book of ASTM 16. F.T. Starr, Carbon and High Performance Fi- quidus Temperature of Glass by the Gradi- Standards, ASTM bres, Directory and Databook, ed. 6, Chap- ent Furnace Method,” C829, Annual Book 6. P.K. Gupta, Glass Fibers for Composite Ma- man & Hall, 1995 of ASTM Standards, ASTM terials, Fibre Reinforcements for Composite 17. “Standard Test Method for Density of Glass 26. “Standard Test Method for Coefﬁcient of Materials, A.R. Bunsell, Ed., Elsevier Pub- by Buoyancy,” C 693, Annual Book of Linear Thermal Expansion of Plastics,” D lishers, 1988, p 19–72 ASTM Standards, ASTM 696, Annual Book of ASTM Standards, 7. J.F. Sproull, Fiber Glass Composition, U.S. 18. “Standard Test Methods for A-C Loss Char- ASTM Patent 4,542,106, 17 Sept 1985 acteristics and Permittivity (Dielectric Con- 27. J.F. Dockum, Jr., Fiberglass, in Handbook 8. W.L. Eastes, D.A. Hofman, and J.W. Win- stant) of Solid Electrical Insulating Materi- of Reinforcement for Plastics, J.V. Milewski gert, Boron-Free Glass Fibers, U.S. Patent als,” D 150, Annual Book of ASTM and H.S. Katz, Ed., Van Nostrand Reinhold 5,789,329, 4 Aug 1998 Standards, ASTM Company, New York, 1987, p 233–286 9. “Advantex Glass Fiber, A New Era in Com- 19. “Standard Test Methods for D-C Resistance 28. R.A. Schoenlaub, “Glass Compositions,” posites Technology—Systems Thinking”, or Conductance of Insulating Materials,” D U.S. Patent 2,334,961, 5 Dec, 1940 Product Bulletin, Owens Corning, 1998 257, Annual Book of ASTM Standards, 29. R.L. Tiede and F.V. Tooley, “Glass Com-10. F. Rossi and G. Williams, A New Era in ASTM position,” U.S. Patent 2,571,074, 23 Nov, Glass Fiber Composites, Proc., 28th AVK 20. “Standard Test Method for Dielectric Break- 1948 Conf. (Baden-Baden, Germany), 1-2 Oct down Voltage and Dielectric Strength of 30. L.L. Clements, Composite Radomes Protect 1997, p 1–10 Solid Electrical Insulating Materials at and Perform, High Performance Composite,11. O.V. Mazurin, M.V. Streltsina and T.P. Commercial Power Frequencies,” D 149, September/October 2000, p 44–47 Shvaiko-Shvaikovskaya, Viscosity of Silica, Annual Book of ASTM Standards, ASTM