Current Opinion in Solid State and Materials Science 4 (1999) 571580

Synthesis, properties and applications of inorganicorganic copolymers (ORMOCER s)

Karl-Heinz Haas*, Herbert Wolter
Fraunhofer-Institut f ur Silicatforschung, Neunerplatz 2, D-97082 Wurzburg, Germany

Abstract Hybrid inorganic-organic polymers based on organically modied heteropolysiloxanes have found widespread attention and application as materials with adjustable properties using tailor-made precursors. The chemical structures of monomers and their modied sol-gel processing method are described. An overview is given for the control of various properties (mechanical, electrical, optical) of the materials on a molecular scale. Successful material developments and industrial applications are described. 2000 Elsevier Science Ltd. All rights reserved.

1. Introduction Organic copolymers dened as polymers derived from more than one species of monomer have found widespread applications as polymer materials. The basic idea behind the formation of copolymers is that properties superior to homopolymers can be achieved. As silicon based copolymers polyorganopolysiloxane block copolymers with mainly linear SiOSi links are well-known [1]. New types of copolymers using monomers which form inorganic network polymers (glass-like) and organic networks have been developed which can be described as inorganicorganic copolymers. They are prepared by the solgel process starting from liquid precursors [2]. This leads to molecular composite materials which cannot be prepared by conventional means like, for example mixing of glass with organic polymers because of temperature restraints. Molecular composites have the potential to combine certain structural properties of different classes of materials in ways not accessible by mixtures of macroscopic phases as this is the case in classical composites (e.g. glass-bre reinforced polymers). The intimate mixture of structural elements which results from their formation by chemical processing (polymerization reactions) can prevent the formation of separate phases. In the case of inorganicorganic hybrid copolymers like ORMOCER s (Trademark of Fraunhofer-Gesellschaft in Germany) the possible combinations of properties are shown in Fig. 1. ORMOCER s belong to the so-called class II hybrid
*Corresponding author. Tel.: 149-931-4100-500; fax: 149-931-4100559. E-mail address: haas@isc.fhg.de (K.-H. Haas).

materials [3] with strong covalent bonds between inorganic and organic moieties. During solgel processing of ORMOCER s the inorganic network is formed rst and the organic crosslinking is the nal curing step. The basic structural elements of ORMOCER s are shown in Fig. 2. The precursors used for these molecular composites can be categorized as follows: Forming inorganic silica type networks based on SiOSi bonds: Type I Forming inorganic oxidic networks other than SiOSi: Type II Modifying the inorganic network by (nonreactive) organic functionalities: Type III Formation of organic networks / crosslinking: Type IV Beside ORMOCER s a wealth of various other types of

Fig. 1. Relationship of ORMOCER s to silicones, organic polymers, glasses and ceramics.

1359-0286 / 00 / $ see front matter 2000 Elsevier Science Ltd. All rights reserved. PII: S1359-0286( 00 )00009-7

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Fig. 2. Structural elements of ORMOCER s (based on type Itype IV precursors).

nanocomposite / molecular composite materials are described in the literature [38]. In the following sections the precursors and the basic network forming reactions of ORMOCER s are described with some properties controlled by the use of distinct structural elements with the focus on mechanical properties. An overview of applications of ORMOCER s will conclude this contribution. 2. Precursors The monomers used for the synthesis of ORMOCER s are silicon alkoxides, organically modied silicon alkoxides, various other metal alkoxides and in some cases also organic monomers. Type I precursors are e.g. Si(OMe) 4 or Si(OEt) 4 , type II precursors are metal alkoxides of Al, Zr, Ti, Sn etc. often used as alkoxides with chelating agents in order to slow down the very high hydrolysis and condensation reaction rates of alkoxides from elements with higher electronegativity than Si. Examples for type III and type IV precursors are shown in Tables 1 and 2. These types of precursors are compounds with alkoxy groups for inorganic network formation and either organic functionalization (type III) or organic crosslinking (type IV). For the formation of organic networks by crosslinking reactions of monomers different from those shown in Table 2, pure organic (not Si-based) monomers like acrylates or di-epoxy-compounds are also used in some cases. In order to widen the possibilities for organic crosslinking reactions multifunctional (meth)acrylate alkoxysilanes have been synthesized ([9,10]). The organic crosslinking can be increased by using two or more reactive organic polymerizable groups per monomeric silane precursor. The high variability of ORMOCER precursors is shown in Fig. 3.

Beside the variation of type and number of organic polymerizable groups (see precursors / 10-13 / in Table 2), the inorganic network forming reactions are controlled by the number of SiOR units. Non-reactive type organic functions (see precursors Table 1) and the type (see precursors / 12,13 / in Table 2) and length of the spacer groups used in the ORMOCER precursors are also useful tools to control the structures formed and the properties connected to them.

3. Basic network forming reactions

3.1. Formation of inorganic network

The reactions for forming the inorganic network of ORMOCER s are the classical inorganic solgel-processing reactions: Hydrolysis: ; SiOR 1 H 2 O ; SiOH 1 ROH

Polycondensation: ; SiOH 1 HOSi ; ; SiOSi ; 1 H 2 O ; SiOH 1 ROSi ; ; SiOSi ; 1 ROH These reactions do not occur consecutively because the polycondensation reactions start as soon as the rst hydrolyzed species are present. The inuence of various pH-conditions, amount of water, solvent, temperature etc. for simple alkoxide compounds is well described [2].

3.2. Organic crosslinking reactions

The second step of ORMOCER synthesis is the organic crosslinking during the nal curing step. Depend-

K.-H. Haas, H. Wolter / Current Opinion in Solid State and Materials Science 4 (1999) 571 580 Table 1 Examples of alkoxysilanes for organic functionalization of inorganic network (type III)

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ing on the nature of the reactive organic groups present in the ORMOCER precursor different reaction types known from organic polymer chemistry can be used to create a linear or a three-dimensional polymer structure connected with the basic inorganic oxidic network. (Meth)acrylate alkoxysilanes can react by radical polymerization or in combination with multifunctional amines by a covalent nucleophilic polyaddition type reaction. Reduced polymerization shrinkage can be achieved through the use of systems polymerizing by a ring-opening polymerization mechanism ([11] and [12]). A radical polyaddition type reaction is observed in thiolene ORMOCER systems [13]. SH-groups are added to the double bonds resulting in a thioether linked ORMOCER network (Precursors / 8 / and / 9 / see Table 2). An important advantage is that in some cases no photoinitiator is necessary leading to enhanced photostability and resistance to weathering. Epoxysilane based ORMOCER systems react by the formation of polyether linkages. These reactions can be catalyzed by the addition of amine compounds like in many conventional organic epoxide systems. In general ORMOCER s can be cured either thermally (1202008C), by UV- / visible light or redox-initiation. Since the inorganicorganic crosslinked materials are duroplastic materials (thermosets) the structural characterization of the cured materials is not straightforward due to

their insolubility. NMR and Raman spectroscopy results especially concerning the reaction of epoxysilane based ORMOCER s have been published recently ([1416]).

4. Shaping processes Due to the formation reaction of ORMOCER s from solution the resulting sols, mainly constituted of organically modied inorganic oligomers, are often used for coatings. The processing of these lacquers is described e.g. in [17]. No special techniques are required for ORMOCER coatings. They can be processed by typical wet-coating techniques (spin-on, spray coating, dip-coating etc.). Typical lm thickness of the cured systems is in the range of 515 mm. The processing of ORMOCER s is also possible as resins which often contain no solvents. Bulk samples, bres, foils / membranes and composites (introduction of llers, see chapter 5) can be prepared. The UV-curing equipment for the preparation of ORMOCER hollow bres is shown in Fig. 4. ORMOCER resins can also be used to create submicron-structures by embossing methods followed by UVcuring. Embossed ORMOCER structures are useful for planar optical waveguides [18] and antireective coatings [19]. Due to the possibility of UV-curing ORMOCER s can also be used for dielectric multilayers and optical

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Table 2 Examples of alkoxysilanes for organic crosslinking / network forming (type IV)

waveguides due to their negative resist behaviour [18,20]. The crosslinked parts of the selectively UV-cured ORMOCER becomes insoluble and the parts not irradiated stay soluble and can be removed by appropriate solvents (e.g. alkaline solutions).

5. Basic properties of ORMOCER s The synthesis principle for the preparation of ORMOCER s has some general consequences concerning their properties. ORMOCER s are homogeneous materi-

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Fig. 3. Schematic structures of multifunctional silanes for ORMOCER synthesis (Precursors: type III organic modication R- and type IV-organic network forming / crosslinking).

als, they are transparent and show duroplastic behaviour due to the organic network / crosslinking (thermosets). Experiments conducted so far to identify inorganic or organic phases by electron microscopy or X-ray methods have resulted in the conrmation of their amorphous behaviour with no detectable phase separation.

5.1. Porosity and density

Classical ORMOCER s with organic crosslinking are

dense materials and show no porosity (,1 m 2 / g according to BET measurements). Organically modied silicates, however, with an appreciable amount of inorganic structures and no organic crosslinking show porosity which can be controlled by the amount of inorganic / organic structures [21]. The density of ORMOCER lies in the range of 1.1 and 1.6 g / cm 3 which is slightly above the range for organic polymers, but well below the density of oxide materials (e.g. SiO 2 52.2 g / cm 3 ). Some basic relationships between density and the amount of organic crosslinking /

Fig. 4. UV-curing equipment for manufacturing of ORMOCER hollow bres (including electron micrograph of an ORMOCER hollow bre).

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modication of the silica network have shown that density decreases with increasing amount of network modifying organic elements (based on type III precursors) and increases with increasing amount of heterometallic oxide structures (based on type II precursors) [22].

compounds can also be used as low shrinkage polymerization materials with excellent mechanical properties [12].

5.3. Mechanical properties 5.3.1. Young s-modulus and thermal expansion coefcient The mechanical and thermomechanical properties (Youngs modulus and thermal expansion coefcient) of ORMOCER bulk materials can be controlled by the amount of inorganic and organic network density and by the spacer-length connecting the inorganic and organic crosslinking sites of bifunctional monomers (see Fig. 3). As an example Fig. 5 shows the inuence of the organic crosslinking density of various multi(meth)acrylate based ORMOCER s on Youngs modulus and the thermal expansion coefcient [24]. As can be expected Youngs modulus increases with increasing organic crosslinking density by using various multi(meth)acrylate alkoxysilane precursors. At the same time the thermal expansion coefcient decreases. The correlation between the number of inorganic network modifying SiC bonds and the thermal expansion coefcient clearly shows [22] the increase of the thermal expansion coefcient at higher amounts of SiC bonds containing ORMOCER s (type III and IV precursors). The mechanical data of SiO 2 / SiO(CH 3 ) 2 type materials, which were prepared by cocondensation of TEOS with polydimethylsiloxaneoligomers (PDMS) [25] shows another example for the variability of Youngs modulus between rubbery materials at high PDMS contents and hard materials at low PDMS contents. However in this

5.2. Shrinkage during curing process

One basic drawback for preparing materials by solgel processing especially in the case of bulk materials is their high volume shrinkage (more than 50%) during removal of the solvents and the curing / network densifying steps. This often leads to mechanical stresses e.g. in thicker coatings, laminates or molded articles (bulk materials). Loss of dimensional precision (problems with near-netshape processing), crack formation, reduced mechanical stability, delamination or other defects may be the consequence. The use of organic crosslinking reactions as the actual curing step to form the inorganicorganic copolymer structure of ORMOCER s makes this shrinkage much less pronounced due to the pre-formation of the inorganic SiOSi network. Polymerization of (meth)-acrylate alkoxysilane based ORMOCER s results in a dramatically reduced shrinkage (28 Vol.%) as compared to pure organic polymerized (meth)-acrylates (often above 20 Vol.%). By the incorporation of llers a further shrinkage reduction is possible. In some cases near zero-shrinkage ORMOCER s can be obtained by using spiroorthoester silanes (Precursor / 12 / see Table 2) with a volume change during the polymerization step of below 0.5% [11]. Norbornene type silanes in combination with thiolene type polyaddition

Fig. 5. Youngs modulus and thermal expansion coefcient of bulk ORMOCER s based on the variation of the number and type of organic polymerizable group of multi(meth)acrylate alkoxysilanes [24].

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case some porosity remains at high amounts of SiO 2 , since the densifying reactions for the inorganic SiOSi network cannot be completed due to temperature restraints. The variability of mechanical data of multiacrylate based ORMOCER s is further increased due to the use of precursors with different spacer lengths between the inorganic and organic network forming groups as shown in Fig. 6. A drastic increase of Youngs modulus from 70 MPa to more than 2000 MPa can be detected by decreasing the spacer length from 20 to 11 atoms connecting inorganic and organic crosslinking sites. Using various types of multi(meth)acrylate alkoxysilane precursors a range of Youngs moduli from around 1 MPa up to 4000 MPa and thermal expansion coefcients from 184 to 67310 26 K 21 (temperature range: 0508C) can be covered [10,24]. The mechanical properties of ORMOCER s can be further modied by using llers of various types and amounts. The thermal expansion coefcient can be lowered to values of 17310 26 K 21 and the Youngs modulus increased up to values of around 17000 MPa at ller contents of 79 wt.%.

thermally curable types showing higher abrasion resistance. The inuence of heteroatoms (Al, Zr, Ti) was investigated in epoxysilane-based ORMOCER s showing that AlO containing ORMOCER s show the highest abrasion resistance [27,28]. Another interesting result concerning epoxysilane-based coatings on polycarbonate substrates was presented by [29]. There it was shown that in contrast to other expectations the Youngs modulus of epoxysilane compositions containing nano-silica particles was lower than in compositions based on epoxysilaneSi(OEt) 4 cocondensates, the latter being real molecular composite materials.

5.4. Optical properties

ORMOCER s are colourless materials showing no absorption in the visible spectrum. The refractive index depends especially on heteroelements (Ti, Zr) used in the ORMOCER compositions. Increasing e.g. the amount of ZrO or TiO-containing structures in epoxysilane based ORMOCER s also increases the refractive index from 1.48 up to 1.68 [30]. Bulk materials based on multiacrylate alkoxysilanes with various spacer groups containing no heteroelements also have been developed with the possibility to increase the refractive index from 1.52 with linear aliphatic to 1.56 with aromatic or 1.60 with halogenated aromatic spacer groups [31]. A decrease of the refractive index of ORMOCER systems at optical wavelengths (to around 1.45) is possible using special multifunctional acrylate systems [32] or uorinated silanes. The use of specially designed peruorarylsilanes ([33] and [34]) leads

5.3.2. Abrasion resistant coatings ORMOCER s are especially useful as abrasion resistant coatings for various substrates [26,27]. Abrasion resistance is often characterized by the taber-abraser method, measuring the increase in haze on transparent substrates if their surface is treated by an abrader wheel. The lower the increase in haze, the higher is the abrasion resistance of the respective coating. For ORMOCER s thermally and UVcurable coatings are available for abrasion resistance, the

Fig. 6. Youngs modulus and thermal expansion coefcient of bulk ORMOCER s based on multiacrylate alkoxysilanes with various spacer lengths dened as number of atoms between inorganic and organic network forming groups [24].

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to very low absorption losses (,0.3 dB / cm) in the NIRregime at 1310 and 1550 nm (optical communication range).

5.4.1. Electric and dielectric properties Most ORMOCER s are highly insulating materials with bulk resistivities in the range of 10 13 10 16 V cm. Therefore they show good passivation properties for electronic applications [35,36], due to their good adhesion to most of the interconnection materials and good barrier properties. Their low dielectric constant (around 3) makes them good candidates for interlayer dielectrics in electrical and optical interconnection technology [18]. Some special ORMOCER types can be synthesized with ion-conduct1 1 ing properties for Li and H -ions. In these cases anions are covalently bound to the inorganic / organic network of ORMOCER s in order to generate mechanically stable solid polymer ion conductors ([37] and [20]). 5.4.2. Surface properties and polarity Since ORMOCER s have important applications as coating materials, the control of the surface polarity often plays an important role. By choosing polar or unpolar functional groups (type III precursors) the surface energy can be increased or decreased. Using uorosilane modied ORMOCER s hydrophobic and oleophobic surfaces can be generated showing low polar and low dispersive contributions to surface energy. It could be shown that depending on the nature and amount of uorosilanes used PTFE-like surface polarity can be achieved with as little as 1 mol-% of appropriate uorosilane [38]. The incorporation of ionic silanes especially increases the polar contribution of the surface energy, thereby lowering the wetting angle for water (antifogging-effect; [39]) and decreasing the surface resistivity (antistatic behaviour; [28]). Since the polarity modifying units are covalently bound to the inorganicorganic ORMOCER network the stability towards leaching of polar compounds, often found e.g. in antifogging or antistatic-coatings is greatly reduced. Also the basic abrasion resistance of ORMOCER coatings is not adversely affected in most cases. 5.5. Barrier properties and corrosion resistance
Due to the possibility of controlling the inorganic and organic network density and the organic functionality of the ORMOCER s it could be shown that effective barrier layers for avours, gases, water and ions could be prepared by using ORMOCER s ([40] and [17]) as coatings on polymers and glasses and also as corrosion resistant layers for metals [41].

very attractive materials for coating applications are their transparency, their good adhesion to various substrates, their chemical stability and their good abrasion resistance due to the inorganic structures in ORMOCER s [26]. As industrial products two abrasion resistant coatings ([42] based on thermal curing ORMOCER and [13] based on UV-curing thiolene addition type ORMOCER ) and a decorative dish-washer resistant ORMOCER coating on lead-crystal glasses [17] could be realized. Antiadhesive (antisoiling), antifogging, antistatic and antireective coatings with good basic abrasion resistance were also developed (see chapter 4). The use of ORMOCER s as barrier layers for food packaging applications especially in connection with inorganic oxide layers (SiO x ) is another vital area of material development [40]. Further coating applications are in the eld of microsystem technology [18] and as materials for chemical sensors [32,43].

6.2. Bulk materials, composites

As shown in chapter 4 ORMOCER s show an enormous variability to adjust material properties like Youngs modulus, thermal expansion coefcient, gas permeability, refractive index etc. Because of additional advantages like high exural strength and hardness, transparency, comparably low shrinkage during the curing process, biocompatibility (conrmed by cytotoxity tests) and the possibility of incorporation of llers, ORMOCER s and ORMOCER composites are an interesting alternative beside the classical bulk materials (organic polymers, glasses) especially when very complex requirements have to be realized. For example a light curable dental lling composite has been developed meeting the essential invitro requirements necessary for an effective amalgam alternative [9]. Some basic dental applications and properties of ORMOCER s are shown in Fig. 7. Products either using ORMOCER s as one of the matrix components (Denite TM ) or using a functionalized ORMOCER based light-curable dental composite in combination with ORMOCER based bondings (Admira TM ) are on the market. Special carboxy modied ORMOCER s are promising matrix materials for the development of light curable glass ionomer cements [23,24]. Further investigations showed that injection moldable, ame retardant ORMOCER composites with high impact strength are also possible.

6.3. Fibres and foils

Due to the solgel processing of ORMOCER s complex rheological requirements necessary for the bre drawing process can easily be realized. New types of unsupported hollow bres based on ORMOCER s with a mechanical behaviour from brittle glass-like (Youngs modulus 5 GPa) to exible rubber-like (elongation at rupture up to 30%) can be used for membrane and material transport applications. Their properties can be adjusted by

6. Applications

6.1. Coatings
The basic properties of ORMOCER s which make them

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Fig. 7. Application and properties of ORMOCER s as dental materials.

varying the composition, the synthesis parameters of the ORMOCER condensates and the spinning parameters (UV-induced curing, Fig. 4). The oxygen permeability can be varied between 0.02 and 250 barrer (1 barrer5 10 21 cm 3 / cm3s3cm Hg) as well as the dimension of the bres (outer diameter: 90 mm5 mm; wall thickness: 15 mm 22 mm). The manufacturing of solid bres and foils is also possible. The three-dimensional inorganic skeleton of the ORMOCER matrix is an ideal starting-point for manufacturing of inorganic micro- or nanoporous hollow bres by pyrolysis. By varying the types and sizes of the organic units, the concept allows the manipulation of pore size and pore size distribution of the membrane. First investigations lead to SiO 2 hollow bres (outer diameter 95 mm, wall thickness 17 mm) with extremely ne porosity (BET surfaces up to 760 m 2 / g, pore size distribution maximum r max ,0,7 nm, half width ,1 nm and pore volume.70%). Good mechanical properties allow a simple handling for the processing to hollow bre modules.

materials which can be tailored for various applications by controlling their molecular structures. This material synthesis principle based on solgel techniques using bifunctional silane based monomers has left the state of pure scientic interest and has successfully entered industrial applications. Due to the large variability of structural combinations the most fruitful time for ORMOCER applications has just begun and further scientic and industrial interest will surely follow.

References
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6.4. Powders and ( Nano)-particles

ORMOCER s can also be prepared as particles or powders. A modication of mechanical and optical properties (e.g. X-ray absorption for medical applications) of ORMOCER composites is often achieved by the synthesis and incorporation of monodisperse spherical ller particles [44]. SiO 2 and SiO 2 / SnO 2 -core-shell particles were prepared with in-situ functionalized surfaces and diameters adjustable in a range of 50500 nm [45].

7. Conclusion ORMOCER s as inorganicorganic copolymers are

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