806

Organic-inorganic
Yoshiki Chujo

hybrid materials

Composite materials formed by the combination of inorganic materials and organic polymers are attractive for the purpose of creating high-performance or high-functional polymeric materials. Of particular interest is the molecular level combination of two different components that may lead to new composite materials, termed organic-inorganic hybrid materials! Recently, new methods for preparing these hybrid materials have been reported. Some improvements of the properties or modifications of these materials have also been explored from the viewpoint of industrial applications.

Hybrid macromonomers
Cubic silsesquioxanes can be thought of as the smallest silica particles [9]. In other words, silsesquioxane-organic copolymers can be thought of as the models of silica-reinforced hybrid materials. For the preparation of these hybrids, thermally curable and photocurable silsesquioxanes were synthesized according to rhe reaction shown in Figure 1 [lO], which included the hydrosilation reaction of the propargyl group (111. The products of this synthesis can be regarded as hybrid macromonomers.

Addresses Departmentof Polymer Chemistry, Graduate School of Engineering,

Kyoto University, Yoshida, Sakyo-ku. Kyoto 606-01, Japan; e-mail: chujo@chujo.synchem.kyoto-u.ac.jp Current Opinion in Solid State 6 Materials Science 1996, 1:806-8 11 0 CurrentChemistry Ltd ISSN 1359-0286

Heteropolysiloxanes
Sol-gel methods provide a versatile way to prepare functionalized inorganic materials under mild conditions. Various metal alkoxide precursors can be used in the sol-gel reaction to give the corresponding metal oxide inorganic material. Silica, alumina, titania, and zirconia are the most popular inorganic components for hybrid materials due to their commercial availability as alkoxide precursors and also to the feasibility of the sol-gel reaction. An exampIe of organic functionalization of silica gel by a sol-gel method is the preparation of transparent monolithic gels by the reaction of diethylphosphatoethyltriethoxysilane and tetraethoxysilane [ 121. The highest SIP concentration that could be introduced in these mixed organic-inorganic systems in order to obtain monolithic transparent gels was found to be 30%. Because organophosphorus moieties can efficiendy extract many types of metal ions, the hybrid materials containing phosphoryl groups can be applied in the preparation of facilitated transport membranes.

Introduction
We cannot exist without commodiry materials such as wood, metals, plastics and glass, that make our lives much more enjoyable. Some combinations among these materials are known as composite materials. Examples of such materials are inorganic fillers in plastics, or organic coatings on the surface of metals. In composite materials, the interface between two different materials is a very important feature of their durability or mechanical properties. In other words, the concept of these composite materials is paste togetherto form a material with improved properties. The concept of molecular level mixing between two different materials can also be considered. Since the late 198Os, molecular level combination between organic polymers and inorganic materials has been of interest. Review articles concerning hybrid materials have been reported by Saegusa and me [ 11, Sanchez and co-workers [2,31, Schubert et a/. [4], Novak [5], Loy and Shea [6], Mark [7], and others [S]. During this period, the study of organic-inorganic hybrid materials focused on the following points: firstly exploration of new preparative methodology for hybrid materials; secondly, new combinations between different materials; thirdly, functionalizacion of hybrid materials; and fourthly, modification of hybrids for industrial applications. This review describes such relevant interesting examples reported during 1995 and 1996, some of which include rhe classical composite materials. The composite materials described here are believed to have evolved and will result in interesting molecular hybrid materials in the near future.

Sutfactant

templates

Organically functionalized mesoporous silicas have also been prepared by the sol-gel reaction of tetraethoxysilane and organosiloxanes in the presence of surfactanr templates [ 13**]. Examples of organosiloxanes are phenyltriethoxysilane and ~-octyltrietho~silane. The addition of the surfactant, hexadecyltrimethylammonium bromide at the stage of soI-gel reaction plays an important role in the formation of mesoporous silica {Fig. 2) after extraction with water. The surfactant template controls the size of the pores formed in the mesoporous silica resulting from the reaction. Porous silicas having lS-3OA pore size and 1060-1520m2gf surface area were effectively obtained using this method [13]. The synthesis of hybrid mesoporous silica materials with controlled functionality and hydrophobicity might open up new avenues for catalysis or for organic-inorganic host-guest chemistry.

Heterogeneous

biocatalysts

The entrapment of lipases in hydrophobic sol-gel materials resulted in the formation of highly active, stable

Organic-inorganic

hybrid materials

Chujo

007

Figure 1

(HSiOI.sh
4 equiv. zz
No

(HSiMezOSiOt .ss)a + 4 equiv. Cl Cl _

No

Synthesis of silsesquioxane macromonomers. Reproduced with permission from 11O**l.

and reusable heterogeneous biocatalysts [14*]. The silane component was found to be an important parameter in optimizing the enzymatic activity. For example, Figure 3 shows the dependence of the activity of immobilized hpase in tetramethoxysilane/methyltrim~thoxysi~ane mixed gels on the gel composition. Surprisingly, the immobilized enzyme showed much higher activity than the commercially available one. These results indicate that the alkyl-modified silica gels with hydrophobic character might be more suitable host matrices for Iipases 1151. By varying a range of parameters such as the use of additives, the watensilane ratio, the amount of catafyst, and the structure of silane monomers, ic should be possible to generate tailor-made gels for each lipase. Entrapment of lipases by the sol-gel process has also been performed in the presence of porous glass beads (sintered glass), resulting in the fixation of hybrid materials on the surface of the support and formation of highly active and mechanically stable heterogeneous

biocatalysts [16*]]. For example, the sintered glass was added to the mixture of gel precursors (tetramethoxysiIane/poiy[dimethyisilo~ne]~, an aqueous solution of iipase, poly(viny1 alcohol), and catalytic amounts of NaE By this procedure, more than 95% of the sol-gel materials were selectively attached to the surface of the beads. The biocatalysts can be used as batch or fluid-bed reactors f17].

Hybrid sensors
Organic or inorganic semiconductors have been reported to change their conductivities when exposed to a variety of organic and inorganic vapors. Thus, these materials can be expected to behave as sensors. Composite materials of tin dioxide and derivatives of the conducting polypyrrole [ 18] gave reversible changes in elcccrical resistance at room temperature when exposed to a range of organic vapors 119.1. Composites containing 2.5% polymer by mass were fabricated and exposed to low concentrations of ethanol, methanol, acetone, methyl acetate and ethyl acetate vapors [ZO-231. The composite materials were found to give

808

Polymers

Figure

Preformed polypyrrole and polythiophene were incorporated into clay (montmorillonite) by the interaction of colloidal nanoparticles of rhe polymers with the colloidal, layered host [24*]. This method using a colloid-colioid reaction [ZS], mighr provide a general route to incorporation of intractable polymers within layered host structures that can be exfoliated, such as smeccice clays 1261, meral disulfides, and some metal oxides. These materials have potential to be used as hybrid sensors.

Structure of colloidal silica-poIy (methyl methacryfate) composites

Composite materials of silica and organic polymers are widely employed as structural materials for their properties of high strength and low density. A new generation of hybrid materials prepared by sol-gel methods have also shown promise as optical materials. The silica surface can be modified with silane coupling agents, which improve adhesion between the filler and the organic polymers. Thus, an understanding of the structures and dynamics of interfaces between two components shouid aid in the design of materials, with improved mechanical and optical properties. The composite materials of colloidal silica and poly(merhy1 mechacrylate) have been well characterized by 13C and 29Si MAS NMR spectroscopies jZ7*]. The parent silica was found to have ethoxy groups isolated in the matrix and silanol groups on the surface. The ethoxy groups in the matrix were retained during reaction with 3-trimethoxysilylpropyl methacrylace, while the silanol groups were consumed. In Ehe reaction a Znm layer of the siiane coupling agent was deposited on the surface of the 10.5 nm diameter silica particles. At least 85% of the methacrylate groups copoiymerized with methyl methacrylate to cross-link the silica into the composites.

TEM micrograph of an organically functionalized mesoporous silica formed by a surfactant-extracted, 20 moWo phenyltriethyoxysilane sample. Reproduced with permission from [13**1.

Figure

Vitreophobic

colloids

% MTMS -

Dependence of the activity (A) of immobilized lipase in tetramethoxysilane/methyltrimethoxysilane (MTMS) mixed gels on the gel composition. the relative activity ix) is defined as n {irnmob~lzed enzymefln (commercial enzyme), where n IS the initial rate of reaction. Reproduced with permission from [39].

more

significant

and

reversible

decreases

in

electrical

with sensors constructed solely of tin dioxide or polypyrrole. These materials could be used in the quality control of foodstuffs, specifically in the early detection of soft rot in potato cubers.
resistance in comparison

In general, gold metal has very little affinity for silica because it does not have an oxide film on its surface. Previous attempts co overcome this vitreophobic character involved the hecerocoagulation of gold colloids on silica coiloids dispersed in water [28]. A new approach was reported [29*.] using silane coupling agents (such as 3-aminopropyltrime~hoxysiIane) as surface primers, which are known to complex strongly with gold metal. Thus, gold colloids were homogeneously coated with silica via a three-step deposition process: the hydrolysis of the surface-bonded siloxane moieties to form silane triols; sodium silicare solution was added to this dispersion, which formed a thin, dense and relatively homogeneous silica layer around the particles; and the. resulting dispersion was then transferred into ethanol, where further growth of the particles was achieved (as a consequence of the hydrolysis of tetraethoxysilane and condensation of the resulting silanol groups). As a result, smooth. monodisperse spherical silica particles with gold cores placed precisely at their centers were obtained. This

Organic-inorganic

hybrid materials

Chujo

309

method can be applied to other kinds of colloids which have typically been difficult to coat with silica, such as silver, copper and semiconductor particles.

Figure 4

Abrasion-resistant

materials

Some hybrid materials exhibit abrasion resistance in addition to optical clarity [30-331. High abrasive resistance can be attributed to the Si-0-Si inorganic backbone structure of the hybrids along with the high level of cross-linking. These abrasion-resistant hybrid materials have been prepared by the sol-gel method using tetramethoxysilane or tetraethoxysilane in the presence of low molecular weight organics such as diethylenetriamine, 3,3-iminobispropylamine, glycerol, ethylene glycol, butanediol, hexanediol, and resorcinol [34*]. The hybrid materials were spincoated onto the surface of a bisphenol-A polycarbonate or a diallyl diglycol carbonate resin. The coating thickness were found to be either 3-5 microns for a single coating or 10-12 microns for double coating. The adhesion between coating and substrate was greatly improved by treating the polymeric substrate surface with a primer solution of 3-aminopropyltriethoxysilane. In addition to this, these coating materials exhibited excellent abrasion resistance and have potential applications as coating materials for eyeglass lenses and other polymeric products. Low volume shrinkage One of the inherent problems in the conventional sol-gel process is that it promotes an exceedingly large volume shrinkage, as a consequence of the removal of a large amount of excess solvent and the removal of small molecules, such as water and alcohol. This volume shrinkage can sometimes reach 75% or higher. Recently, polyacrylate-silica hybrids were prepared by sol-gel reactions using silicates having a polymerizable acrylate monomer moiety, in which the volume shrinkage was significantly reduced [35-381. Very recently, a fast and convenient synthetic technique to prepare crack-free, transparent, monolithic vinyl polymer-silica hybrid sol-gel materials with significantly reduced volume shrinkages has been reported [39**]. The principle of this procedure is the acid-catalyzed sol-gel reaction of tetraethoxysilane in the presence of sol-gel reactive vinyl monomers (such as Z-hydroxyethyl methacrylate) to form oligomeric/polymeric silicate colloids 140-441. The silanol groups in the silicate colloids react with the alcohol groups in the monomer .to form a covalent linkage between the organic component and inorganic one. After the removal of a large amount of the solvent, the resulting nonvolatile fluid could be cast into various molds. The free-radical polymerization of the vinyl monomers could then be initiated, either by heating in the presence of thermal initiators or by exposing the system to light. The volume shrinkage from the processible sol to the final product was only 6-20% for the hybrid materials with up to 47 wt% silica content, as shown in Figure 4.

50403020lo0 10
I I I I

30

50

70 (wt-%)

90

SiOg Content

Relationship between the volume shrinkage and the compositions of the polyacrylate-silica hybrid sol-gel materials. Reproduced with permission from [39**1.

Fiber-reinforced

polymer hybrids

Polyethylene fiber or carbon fiber can be used as one of the reinforcing fibers in hybrid composites. Composites based on thermoplastic polymeric matrices potentially offer several advantages compared with those based on thermosetting resins [45]. Unidirectional laminates were prepared from polyethylene fiber, carbon fiber and the hybrid formed by them reacted with partially polymerized methyl methacrylate well below the softening point of polyethylene [46]. Addition of polyethylene fiber ply/plies to the tension side resulted in structural hybrid laminates exhibiting a significantly higher ultimate flexural strength in comparison with the system where carbon fiber ply/plies were present on the tension side. The flexural fracture mode of carbon fiber could be minimized by placing polyethylene fiber ply/plies at the outermost side of these hybrid laminates. To improve the mechanical properties of glass fiber-poly (phenylene sulfide) composite materials [47], silane coupling agents were used to modify the glass fiber surfaces [48]. The interlaminar shear strength and the flexural strength of the silane-treated composites increased in comparison with the untreated one [49]. Silver powder has also been used as a filler for polypropylene composites to improve mechanical properties, such as tensile and flexural properties, or impact strength [SO]. Tensile modulus, strength, and elongation at break were found to decrease with the incorporation of silver and decrease further with an increase in silver concentra-

810

Polymers

tion. These results may be a result of the rigid and incompressive nature of silver powders, which did not leave sufficient space for compressive deformation of polypropylene to take effect.

The hybrid materials obtained consist of Si-C stable toward hydrolysis. 13. ..

and P-C

bonds, which are

Conclusion
Organic-inorganic hybrid materials are expected to provide many possibilities as new composite materials. The hybrid materials usually show properties intermediate between those of plastics and glasses (ceramics). Accordingly, hybrids can be used to modify organic polymer materials or to modify inorganic glassy materials. In addition to these characteristics, the hybrid materials can be considered as new composite materials that exhibit very different properties from their original components (organic polymer and inorganic materials), especially in the case of molecular level hybrids. In other words, hybrid materials should be considered as next-generation composite materials that will encompass a wide variety of applications.

Burkett SL, Sims SD, Mann S: Synthesis of hybrid inorganic-organic mesoporous silica by co-condensation of siloxane and organosiloxane precursors. Chem Commun 1996:1367-l 368. The surfactant added is very important as it acts as a template to control the pore size of the porous silica formed. Reetz MT, Zonta A, Simpelkamp J: Efficient heterogeneous biocatelysts by entrapment of lipases in hydrophobic sol-gel materials. Angew Chem lnt Ed 1995, 34:301-303. The immobilized lipase showed much higher activity than the commercial one. This heterogeneous biocatalyst can be used for the kinetic resolution of 1 -phenylethanol producing much higher enatiomerically pure products. 15. Schwertfeger F, Glaubitt W, Schubert U: Hydrophobic aerogels from tetramethoxysilane/methyltrimethoxysilane mixtures. J Non-Cry& Solids 1992, 145:05-09. 14. ..

Reetz MT, Zonta A, Simpelkamp J, Kijnen W: In situ fixation of lipase-containing hydrophobic sol-gel rneterials on sintered glass - hlghly efficient heterogeneous biocetelysts. Chem Commun 1996:1397-l 396. Fixation of lipaae-containing hybrid materials on sintered glass resulted in the formation of highly active and mechanically satble heterogeneous biocatalysts, which is very useful in their applications. 1 7. 16. 19. . Avnir D: Organic chemistry within ceramic metrices: Doped sol-gel materials. Accounts Chem Res 1995, 28:326-334. Miasik JJ, Hooper A, Tofield BC: Conducting polymer gas sensors. J Chem Sot faraday Tmns 1 1986, 82:1117-l 126.

16. .

References and recommended

reading

Papers of particular interest, published within the annual period of review, have been highlighted as: .
l

of special interest of outstanding interest Chujo Y, Saegusa T: Organic polymer hybrids with silica gel formed by means of the sol-gel method. Adv Polym Sci 1992, loo:1 l-29. Sanchez C, Ribot F: Design of hybrid organic-inorganic materials synthesized via sol-gel chemistry. New J Chem 1994, l&l 007-l 047. Judeinstein P, Sanchez C: Hybrid organic-inorganic materials: land of multidisciplinarity. J Mater Chem 1996, 6:51 l-525. Schubert U, Hiising N, Lorenz A: Hybrid inorganic-organic materials by sol-gel processing of organofunctional metal alkoxides. Chem Mater 1995, 7:201 O-2027. Novak BM: Hybrid nanocomposite materials between inorganic glasses and organic polymers. Adv Mater 1993, 6:422-433. Loy DA, Shea KJ: Bridged polysilsesquioxanes. Highly porous hybrid organic-inorganic materials. Chem Rev 1995, S&1431 1442. Mark JE: Novel reinforcement techniques for elastomers. Polym Sci Appl Polym Symp 1992,60:273-262. J Appl a

Lacy Costello BPJ, Evans P, Ewen RJ, Honeyboume CL, Ratcliffe M: Novel composite organic-inorganic semiconductor sensors for the quantitative detection of terget organic vapours. J Mater Chem 1996,6:299-294. The combination of organic and inorganic semiconductors should be pointed out to give reversible changes in electrical resistance. 20. Maekawa T, Tamaki J, Miura N, Yamazoe N, Matsushima S: Development of tin dioxide-based ethanol gas sensor. Sensors Actuators B Chem 1992, 9:63-69. Gardner JW, Hines EL, Tang HC: Detection of vapors and odors from a multisensor array using pattern-recognition techniques 2. Artificial neural networks. Sensors Actuators B Chem 1992, 9:9-l 5. Persaud K, Dodd G: Analysis of discrimination mechanisms in the mammalian olfactory system using a model nose. Nature 1962,299:352-355. Nenov T, Yordanov S: Ceramic sensor device materials. Actuators B Chem 1992, 8:117-l 22. Sensors

1.

21.

2.

22.

3. 4.

23. 24. .

5. 6.

Oriakhi CO, Lemer MM: Poly(pyrrole) and poly(thiophene)/clay nanocomposites via latex-colloid interaction. Mater Res Bull 1995, 30:723-729. Clays are also used as an inorganic component for the preparation of hybrid materials. The direction of the components in the matrix can sometimes be controlled in these materials. 25. Lemmon JP, Lemer MM: Preparation and characterization of nanocomposites of polyethers and molybdenum disulfide. Chem Mater 1994, 6:207-210. Vaia R, lshii H, Giannelis E: Synthesis and properties of twodimensional nanostructures by direct intercalation of polymer melts in layered silicates. Chem Mater 1993, 5:1694-l 696.

7.

26.

0.

Mark JE, Lee CY, Bianconi PA (Eds): Hybrid organic-inorganic composites. Washington; American Chemical Society; 1995. [American Chenical Society Symposium Series, vol 565.1 Btirtsch M. Bomhauser P, Cairaferri G, lmhof R: HsSisOl.z: a model for the vibrational structure of zeolite A. J Phys Chem 1994, S&261 7-2631.

9.

Sellinger A, Laine RM: Silsesquioxanes as synthetic platforms. Thermally curable and photocurable inorganic/organic hybrids. Macromolecules 1996, 29:2327-2330. The product in this study can be used as the so-called macromonomer for the preparation of new organic-inorganic hybrid materials. 11. Sellinger A, Laine RM, Chu V, Viney C: Palladium- and platinum-catalyzed coupling reactions of allyfoxy aromatics with hydridosilanes and hydridosiloxanes: novel liquid crystelline/organosilane materials. J Polym Sci Polym Chem 1994, 32:3069-3069. Cardenas A, Hovnanian N, Smaihi M: Sol-gel formation of heteropolysiloxanes from diethylphosphatoethyltriethoxysilane and tetraethoxysilane. J Appl Polym Sci 1996, 60:2279-2266.

10 ..

Joseph R, Zhang S, Ford Wl: Structure and dynamics of a colloidal silica-poly(methyl methacrylate) composite by 1% and *sSi MAS NMR spectroscopy. Macromolecules 1996, 29:1305-l 312. Spectroscopic characterization is very important in the elucidation the structure of hybrid materials. 27. . 26. Liz-MarzPn LM, Philipse AP: Synthesis and optical properties of gold-labeled silica particles. J Colloid Interface Sci 1995, 176~459-466.

Liz-Marz&n LM, Gieraig M, Mulvaney P: Homogeneous silica coating of vitreophobic colloids. Chem Commun 1996:731-732. The results in this paper present the preparation of new three-component hy brid materials consisting of organic polymers, inorganic materials, and metal colloids. 29. .. 30. Bet&et C, Wilkes GL: Optically abrasion resistent materials using a sol-gel approach. Amer Chem Sot Po/ym Prep 1992, 33:266-297.

12. .

Organic-inorganic

hybrid materials

Chujo

811

31.

Tamami B, Bet&et G, Wilkes GL: New ceremer hiih opthi abrasion resistant transparent coattng mabrtals based on functtonalyzad malatmide and a disc-aminophenyl)phos~ine oxtde compound. PO&~ 311/l1@93,30:3@-45. Temami B, Bet&et C, Wilkes GL: Synthesis and application of abrasbn resistant coattng matartais based on functionalped bis and trts maiaimides. Poijm 6ufllQ93,9(f:393-3QS. Wang B, Wilkes GL: Novel hybrid inorganic-organic abrasionresistant coattngs preparad by a sol-gel process. J Mecfomof Sci Pure Appi Chem 4694, A31 :249-260.

41.

Wei Y, Yang D, Tang L, Hutchins MK: Syntf~a&, chamcterization, and properttes of new polystyrene-silica hybrid sol-gel materials. J Meter Res 1993,&l 143-l 162. Wei Y, Yang 0, Tang L: Synthesis of new poiyacryionttrile-silica hybrid sol-gel materials and their thermal proparties. Makromol Chem Repid Commun f 993,14:273-278. Wei Y, Wang W, Yang D, Tang L: Synthesis of water-soluble polyacrylics modified silica sol-gal materials. Chem Mater 1994, 6:1737-l 741. Wei Y, Yeh J, Jin D, Jia X, Wang J: Compositas of elactronlcally conductive poiyaniiine with polyacrylata-silica hybrtd sol-gel meterirrlt Chem Meter 19@5,7:969-974. Kodokien GKA, Kinloch AJ: Sutfaca pmtmatment and adhesion of tharmopiasttc fiber composites. J Meter SW Lett 1988, 7:625-627.

42.

32.

33.

43.

Wen J, Wilkes GL: Noval rbmsion resistant inorganic/organic coating matartais basad on functionslizad die~~ne~ami~, t&carol and dids. Atner Chem Sac Po&m Prep 1SQS, 36:429-430. The advantage of hwd materialsas sbrasion-resistantcoatings has been w&l demonstratedin this paper. 36. Uleworth MW, Novak EM: Mutually interpenetrating inorganic-organic networks. New routas into nonshrinking ~~~~~7~ matartais. J Am Chem Sot 199 t , : . Novak BM, Davies C: invane organk-inorgantc compostta metertats 2 Fraa-radlcal routas into nonshrtnktng sol-get wmpositaa MactvmoXecules 199 1,24:548 1-5403. Novak BM, Ulsworth MW: %varse* organk-inorganic wmposita materials. High gius content ~n~hdn~ng composite& Mater Sci Eng A IQS3,162:267-284. sol-ad

34. .

44.

45.

46. .

36.

Bandee AN, Saha N: Rexumi behavior of unidirection8l ~~~~e~r~n flbars-PMMA hybrid composite laminates. J Appt PO&m Sci f QSS,80: 139-l 42. -. The combination of an organic polymer end &on tiber produced interesting hybrid materials having a good baiance of flexural behavior. Scobbo 11: Effect of solid-state curing on the viscoeiastic properties of polytphenyfene sulfides. 1 Appl Pobm Sci 1993, 47:2169-2175. Menon N, Blum FD, Dhareni LR: Use of titanate coupling agents in Keviar-phenoiic composltar J Appt PoIym Sci 1994, 54:113-l 23.

47.

37%

48.

38.

Ellswortht&V, Novak BM: *inverse organic-inorganic wmposlte materials 3. High giess wntent %onshrinMng sol-gel composites via poiy(silidc acid esters). Chem Mater 1993,5:839-844.

Wei Y, Jin D, Yang C, Wei G: Synthasts of organic-inorganic hybrid sol-gel matartsls with low volume-shrinkages. Am Chem Sot PO&m Mater Sci Eng 1996,74:244-245. Large volumeshrinka& is cne at the inherent probla in industrialappliition of hybrid materials.This paper desctibea a very convenient and useful technique to overcome this diasdvantage. 39. .. 40. Wei Y, Yang D, back R: Thermal stabiltty and hardness of new poiyacrytata-siiica hybrid sol-gel materials. Mater Lett 1992, 13:261-266.

Jang J, Kim H: Performance improvement of glass ftbarpoiy(phenyiene sulfide) wmposite. / Appl Potym Sci 1906, 60:2297-2306. fiber-reinforced polymer composites have been widely used as high performance materials in aerospace end automotive sppliitions. This paper describes surface modificationd a glass fiber using silane couplingagents. Ghosh K, Maiti SN: Mechanical propartter of siiver-powderfilled potypropyiene composites. J Appl PoIym Sci f 996, 60:323-331. A titanate coupling agent may assist the hybridiition of isotactic polypropylene and silver powder. 60. .

49. .