Hybrid materials are
composites consisting of two constituents at the
nanometer
330px, Different lengths as in respect to the molecular scale.
The nanometre (international spelling as used by the International Bureau of Weights and Measures; SI symbol: nm) or nanometer (American and British English spelling differences#-re ...
or
molecular level. Commonly one of these compounds is
inorganic
In chemistry, an inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds, that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as ''inorganic chemist ...
and the other one
organic in nature. Thus, they differ from traditional composites where the constituents are at the macroscopic (
micrometer Micrometer can mean:
* Micrometer (device), used for accurate measurements by means of a calibrated screw
* American spelling of micrometre
The micrometre ( international spelling as used by the International Bureau of Weights and Measures; ...
to
millimeter
330px, Different lengths as in respect to the electromagnetic spectrum, measured by the metre and its derived scales. The microwave is between 1 meter to 1 millimeter.
The millimetre (American and British English spelling differences#-re, -er, ...
) level. Mixing at the microscopic scale leads to a more homogeneous material that either show characteristics in between the two original
phases or even new properties.
Introduction
Hybrid materials in nature
Many natural materials consist of inorganic and organic building blocks distributed on the nanoscale. In most cases the inorganic part provides mechanical strength and an overall structure to the natural objects while the organic part delivers bonding between the inorganic building blocks and/or the rest of the
tissue. Typical examples include
bone
A bone is a Stiffness, rigid Organ (biology), organ that constitutes part of the skeleton in most vertebrate animals. Bones protect the various other organs of the body, produce red blood cell, red and white blood cells, store minerals, provid ...
and
nacre.
Development of hybrid materials
The first hybrid materials were the paints made from inorganic and organic components that were used thousands of years ago.
Rubber
Rubber, also called India rubber, latex, Amazonian rubber, ''caucho'', or ''caoutchouc'', as initially produced, consists of polymers of the organic compound isoprene, with minor impurities of other organic compounds. Thailand, Malaysia, and ...
is an example of the use of inorganic materials as fillers for organic
polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
. The
sol–gel process
In materials science, the sol–gel process is a method for producing solid materials from small molecules. The method is used for the fabrication of metal oxides, especially the oxides of silicon (Si) and titanium (Ti). The process involves con ...
developed in the 1930s was one of the major driving forces what has become the broad field of inorganic–organic hybrid materials.
Classification
Hybrid materials can be classified based on the possible interactions connecting the inorganic and organic species.
[ ''The Supramolecular Chemistry of Organic-Inorganic Hybrid Materials'' , Knut Rurack, Ramon Martinez-Manez , Eds., Wiley 2010 https://onlinelibrary.wiley.com/doi/book/10.1002/9780470552704 ] ''Class I'' hybrid materials are those that show weak interactions between the two phases, such as
van der Waals,
hydrogen bonding
In chemistry, a hydrogen bond (or H-bond) is a primarily electrostatic force of attraction between a hydrogen (H) atom which is covalently bound to a more electronegative "donor" atom or group (Dn), and another electronegative atom bearing a l ...
or weak
electrostatic
Electrostatics is a branch of physics that studies electric charges at rest ( static electricity).
Since classical times, it has been known that some materials, such as amber, attract lightweight particles after rubbing. The Greek word for amb ...
interactions. ''Class II'' hybrid materials are those that show strong chemical interactions between the components such as
covalent bonds
A covalent bond is a chemical bond that involves the sharing of electrons to form electron pairs between atoms. These electron pairs are known as shared pairs or bonding pairs. The stable balance of attractive and repulsive forces between atoms ...
.
Structural properties can also be used to distinguish between various hybrid materials. An organic
moiety
Moiety may refer to:
Chemistry
* Moiety (chemistry), a part or functional group of a molecule
** Moiety conservation, conservation of a subgroup in a chemical species
Anthropology
* Moiety (kinship), either of two groups into which a society is ...
containing a functional group that allows the attachment to an inorganic network, e.g. a trialkoxysilane group, can act as a ''network modifier'' because in the final structure the inorganic network is only modified by the organic group. Phenyltrialkoxysilanes are an example for such compounds; they modify the silica network in the sol–gel process via the reaction of the trialkoxysilane group without supplying additional functional groups intended to undergo further chemical reactions to the material formed. If a reactive functional group is incorporated the system is called a ''network functionalizer''. The situation is different if two or three of such anchor groups modify an organic segment; this leads to materials in which the inorganic group is afterwards an integral part of the hybrid network. The latter type of system is known as ''network builder''
Blends are formed if no strong chemical interactions exist between the inorganic and organic building blocks. One example for such a material is the combination of inorganic clusters or particles with organic polymers lacking a strong (e.g. covalent) interaction between the components. In this case a material is formed that consists for example of an organic polymer with entrapped discrete inorganic moieties in which, depending on the functionalities of the components, for example weak crosslinking occurs by the entrapped inorganic units through physical interactions or the inorganic components are entrapped in a crosslinked polymer matrix. If an inorganic and an organic network interpenetrate each other without strong chemical interactions, so called interpenetrating networks (IPNs) are formed, which is for example the case if a sol–gel material is formed in presence of an organic polymer or vice versa. Both materials described belong to class I hybrids. Class II hybrids are formed when the discrete inorganic building blocks, e.g. clusters, are covalently bonded to the organic polymers or inorganic and organic polymers are covalently connected with each other.
Distinction between nanocomposites and hybrid materials
The term
nanocomposite
Nanocomposite is a multiphase solid material where one of the phases has one, two or three dimensions of less than 100 nanometers (nm) or structures having nano-scale repeat distances between the different phases that make up the material.
The id ...
is used if the combination of organic and inorganic structural units yield a material with composite properties. That is to say that the original properties of the separate organic and inorganic components are still present in the composite and are unchanged by mixing these materials. However, if a new property emerges from the intimate mixture, then the material becomes a hybrid. A macroscopic example is the mule, which is more suited for hard work than either of its parents, the horse and the donkey. The size of the individual components and the nature of their interaction (covalent, electrostatic, etc.) do not enter into the definition of a hybrid material.
Advantages of hybrid materials over traditional composites
* Inorganic clusters or nanoparticles with specific optical, electronic or magnetic properties can be incorporated in organic polymer matrices.
* Contrary to pure solid state inorganic materials that often require a high temperature treatment for their processing, hybrid materials show a more polymer-like handling, either because of their large organic content or because of the formation of crosslinked inorganic networks from small molecular precursors just like in polymerization reactions.
* Light scattering in homogeneous hybrid material can be avoided and therefore optical transparency of the resulting hybrid materials and nanocomposites can be achieved.
Synthesis
Two different approaches can be used for the formation of hybrid materials: Either well-defined preformed building blocks are applied that react with each other to form the final hybrid material in which the precursors still at least partially keep their original integrity or one or both structural units are formed from the precursors that are transformed into a new (network) structure. It is important that the interface between the inorganic and
organic materials which has to be tailored to overcome serious problems in the preparation of hybrid materials. Different building blocks and approaches can be used for their preparation and these have to be adapted to bridge the differences of inorganic and organic materials.
Building block approach
Building blocks at least partially keep their molecular integrity throughout the material formation, which means that structural units that are present in these sources for materials formation can also be found in the final material. At the same time typical properties of these building blocks usually survive the matrix formation, which is not the case if material precursors are transferred into novel materials. Representative examples of such well-defined building blocks are modified inorganic clusters or nanoparticles with attached reactive organic groups.
Cluster compounds often consist of at least one functional group that allows an interaction with an organic matrix, for example by copolymerization. Depending on the number of groups that can interact, these building blocks are able to modify an organic matrix (one functional group) or form partially or fully crosslinked materials (more than one group). For instance, two reactive groups can lead to the formation of chain structures. If the building blocks contain at least three reactive groups they can be used without additional molecules for the formation of a crosslinked material.
Beside the molecular building blocks mentioned, nanosized building blocks, such as particles or nanorods, can also be used to form nanocomposites. The building block approach has one large advantage compared with the in situ formation of the inorganic or organic entities: because at least one structural unit (the building block) is well-defined and usually does not undergo significant structural changes during the matrix formation, better structure–property predictions are possible. Furthermore, the building blocks can be designed in such a way to give the best performance in the materials’ formation, for example good solubility of inorganic compounds in organic monomers by surface groups showing a similar polarity as the monomers.
In recent years many building blocks have been synthesized and used for the preparation of hybrid materials. Chemists can design these compounds on a
molecular scale with highly sophisticated methods and the resulting systems are used for the formation of functional hybrid materials. Many future applications, in particular in nanotechnology, focus on a bottom-up approach in which complex structures are hierarchically formed by these small building blocks. This idea is also one of the driving forces of the building block approach in hybrid materials.
In situ formation of the components
The in situ formation of the hybrid materials is based on the chemical transformation of the precursors used throughout materials’ preparation. Typically this is the case if organic polymers are formed but also if the sol–gel process is applied to produce the inorganic component. In these cases well-defined discrete molecules are transformed to multidimensional structures, which often show totally different properties from the original precursors. Generally simple, commercially available molecules are applied and the internal structure of the final material is determined by the composition of these precursors but also by the reaction conditions. Therefore, control over the latter is a crucial step in this process. Changing one parameter can often lead to two very different materials. If, for example, the inorganic species is a silica derivative formed by the sol–gel process, the change from base to acid catalysis makes a large difference because base catalysis leads to a more particle-like microstructure while acid catalysis leads to a polymer-like microstructure. Hence, the final performance of the derived materials is strongly dependent on their processing and its optimization.
In situ formation of inorganic materials
Many of the classical inorganic solid state materials are formed using solid precursors and high temperature processes, which are often not compatible with the presence of organic groups because they are decomposed at elevated temperatures. Hence, these high temperature processes are not suitable for the in situ formation of hybrid materials. Reactions that are employed should have more the character of classical covalent bond formation in solutions. One of the most prominent processes which fulfill these demands is the sol–gel process. However, such rather low temperature processes often do not lead to the thermodynamically most stable structure but to kinetic products, which has some implications for the structures obtained. For example, low temperature derived inorganic materials are often
amorphous
In condensed matter physics and materials science, an amorphous solid (or non-crystalline solid, glassy solid) is a solid that lacks the long-range order that is characteristic of a crystal.
Etymology
The term comes from the Greek ''a'' ("wi ...
or
crystallinity is only observed on a very small length scale, i.e. the nanometer range. An example of the latter is the formation of metal nanoparticles in organic or inorganic matrices by reduction of metal salts or organometallic precursors.
Some methods of in situ formation of inorganic materials are:
*
Sol-gel process
* Nonhydrolytic sol–gel process
* Sol–gel reactions of non-silicates
Formation of organic polymers in presence of preformed inorganic materials
If the organic polymerization occurs in the presence of an inorganic material to form the hybrid material one has to distinguish between several possibilities to overcome the incompatibility of the two species. The inorganic material can either have no surface functionalization but the bare material surface; it can be modified with nonreactive organic groups (e.g. alkyl chains); or it can contain reactive surface groups such as polymerizable functionalities. Depending on these prerequisites the material can be pretreated, for example a pure inorganic surface can be treated with surfactants or silane coupling agents to make it compatible with the organic monomers, or functional monomers can be added that react with the surface of the inorganic material. If the inorganic component has nonreactive organic groups attached to its surface and it can be dissolved in a monomer which is subsequently polymerized, the resulting material after the organic polymerization, is a blend. In this case the inorganic component interact only weakly or not at all with the organic polymer; hence, a class I material is formed. Homogeneous materials are only obtained in this case if agglomeration of the inorganic components in the organic environment is prevented. This can be achieved if the interactions between the inorganic components and the monomers are better or at least the same as between the inorganic components. However, if no strong chemical interactions are formed, the long-term stability of a once homogeneous material is questionable because of diffusion effects in the resulting hybrid material. The stronger the respective interaction between the components, the more stable is the final material. The strongest interaction is achieved if class II materials are formed, for example with covalent interactions.
Hybrid materials by simultaneous formation of both components
Simultaneous formation of the inorganic and organic polymers can result in the most homogeneous type of interpenetrating networks. Usually the precursors for the sol–gel process are mixed with monomers for the organic polymerization and both processes are carried out at the same time with or without solvent. Applying this method, three processes are competing with each other:
(a) the kinetics of the hydrolysis and condensation forming the inorganic phase,
(b) the kinetics of the polymerization of the organic phase, and
(c) the thermodynamics of the phase separation between the two phases.
By tailoring the kinetics of the two polymerizations in such a way that they occur simultaneously and rapidly enough, phase separation is avoided or minimized. Additional parameters such as attractive interactions between the two moieties, as described above can also be used to avoid phase separation.
One problem that also arises from the simultaneous formation of both networks is the sensitivity of many organic polymerization processes for sol–gel conditions or the composition of the materials formed. Ionic polymerizations, for example, often interact with the precursors or intermediates formed in the sol–gel process. Therefore, they are not usually applied in these reactions.
Applications
* Decorative coatings obtained by the embedding of
organic dye
A dye is a colored substance that chemically bonds to the substrate to which it is being applied. This distinguishes dyes from pigments which do not chemically bind to the material they color. Dye is generally applied in an aqueous solution and ...
s in hybrid coatings.
* Scratch-resistant coatings with hydrophobic or anti-fogging properties.
* Nanocomposite based devices for electronic and optoelectronic applications including
light-emitting diodes
A light-emitting diode (LED) is a semiconductor device that emits light when current flows through it. Electrons in the semiconductor recombine with electron holes, releasing energy in the form of photons. The color of the light (cor ...
,
photodiodes
A photodiode is a light-sensitive semiconductor diode. It produces current when it absorbs photons.
The package of a photodiode allows light (or infrared or ultraviolet radiation, or X-rays) to reach the sensitive part of the device. The packag ...
,
solar cells
A solar cell, or photovoltaic cell, is an electronic device that converts the energy of light directly into electricity by the photovoltaic effect, which is a physical and chemical phenomenon. ,
gas sensors
A gas detector is a device that detects the presence of gases in an area, often as part of a safety system. A gas detector can sound an alarm to operators in the area where the leak is occurring, giving them the opportunity to leave. This type of d ...
and
field effect transistors
The field-effect transistor (FET) is a type of transistor that uses an electric field to control the flow of current in a semiconductor. FETs (JFETs or MOSFETs) are devices with three terminals: ''source'', ''gate'', and ''drain''. FETs control ...
.
* Fire retardant materials for construction industry.
* Nanocomposite based
dental filling
Dental restoration, dental fillings, or simply fillings are treatments used to restore the function, integrity, and morphology of missing tooth structure resulting from caries or external trauma as well as to the replacement of such structure sup ...
materials.
* Composite
electrolyte materials for applications such as solid-state lithium batteries or
supercapacitors.
*
Proton conducting membranes used in
fuel cells.
* Antistatic / anti-reflection coatings
*
Corrosion
Corrosion is a natural process that converts a refined metal into a more chemically stable oxide. It is the gradual deterioration of materials (usually a metal) by chemical or electrochemical reaction with their environment. Corrosion engi ...
protection
* Porous hybrid materials
References
* Guido Kickelbick (Editor), ''Hybrid Materials: Synthesis, Characterization, and Applications'', Wiley, , {{doi, 10.1002/9783527610495
Inorganic-Organic Hybrid Materials
Nanomaterials
Composite materials