Technical Bulletin Fine Particles

Number 11

Basic Characteristics of AEROSIL Fumed Silica

Basic Characteristics and Applications of AEROSIL products

Part 1 in Basic Characteristics and Applications of AEROSIL products was first published in 1967, and was assigned Number 11 in the series of Technical Bulletin Pigments. During the intervening time the text was revised twice, and was made available to a growing readership in new editions. Now the 4th edition of this Number 11 is available in completely new form, made topical in every respect, and brought entirely up to date. It is intended to impart the basic knowledge required to understand AEROSIL products, that is almost 50 years old, and its characteristics. AEROSIL is the trade-mark owned by Degussa AG with 106 registrations in 84 countries throughout the world for a - fumed - highly-dispersed - amorphous - pulverulent synthetic silica. The particle fineness and structure of the AEROSIL fumed silica primary particles are reflected in the application characteristics. Among other advantages, the reactivity of the silanol groups permits an irreversible chemical aftertreatment. Hydrophobic products made-to-order such as, for example, AEROSIL R 972 and AEROSIL R 805 are the result. The present work describes the basic physico-chemical and application characteristics of AEROSIL products. The technical applications of AEROSIL products are discussed. The first edition of this Technical Bulletin Pigments was published by R. Bode, H. Ferch, and H. Fratzscher in Kautschuk + Gummi - Kunststoffe 20, 578 (1967).

Degussa AG Applied Technology AEROSIL

Table of Contents
Page

1. 1.1 1.2 1.2.1 1.2.2 1.2.3 1.2.4 2. 2.1 2.2 2.3 3. 3.1 3.2 3.2.1 3.2.2 3.2.2.1 3.2.2.2 3.3 3.3.1 3.3.2 3.3.3 3.3.4 3.3.5 3.4 3.5 3.5.1 3.5.2 3.5.3 3.6 3.6.1 3.6.2 3.6.2.1 3.6.2.2 3.6.2.3 3.6.3 3.6.3.1 3.6.3.2 3.6.3.2.1 3.6.3.2.2 3.6.3.2.3 3.6.3.3 3.6.3.4

Silicon Dioxide, SiO2 Natural Occurrences Synthetic Silicas Organization Silicas Produced by Degussa Comparison: AEROSIL/Wet Process Silicas AEROSIL Commmercial Products Production Production of Hydrophilic AEROSIL products Production of Highly-dispersed Pyrogenic Special Oxides Chemical Aftertreatment Characteristics Amorphous Structure and Thermostability Particle Fineness and Surface Particle Size and Structure Specific Surface Geometrical Determination of the Specific Surface Determination of the Specific Surface by Adsorption Special Physico-Chemical Data Solubility Thermal Conductivity Nuclear Magnetic Resonance Spectroscopy Behaviour Tribo-Electricity Refractive Index Purity Oxide Mixtures and Mixed Oxides AEROSIL COK 84 AEROSIL MOX 80 and AEROSIL MOX 170 AEROSIL Dispersions Surface Chemistry Two Functional Groups Determine the Chemistry Determination of the Silanol Groups The Lithium Aluminium Hydride Method IR Spectroscopy Morpholine Adsorption Interparticular Interactions Hydrogen Bridge Linkage Moisture Balance Moisture Balance at Room Temperature Aging Moisture Balance at Higher Temperatures Other Adsorption Effects AEROSIL fumed silica as an Acid

6 6 7 7 8 9 10 11 11 12 12 15 15 19 21 27 27 28 29 29 30 31 32 32 32 33 34 35 35 36 36 37 37 38 39 39 40 41 41 42 42 43 44

Page

3.6.4 3.6.4.1 3.6.4.1.1 3.6.4.1.2 3.6.4.2 3.6.4.2.1 3.6.4.2.2 3.6.4.2.3 4. 5. 6. 6.1 6.2 6.3 6.4 6.5 6.6 7. 8. 9.

The Aftertreatment a Chemical Anchoring The Chemical Aftertreatment Some Bibliographic Examples Amination Reactions with Alkoxysilanes Hydrophobic AEROSIL products Conversion from Hydrophilic to Hydrophobic The Chemical Anchoring Dry Water and Aqueous Dispersions with Hydrophobic AEROSIL products Statistical Quality Control Types of AEROSIL products Applicational Effects Reinforcement Thickening Antisetting Agent Free Flow Thermal Insulation AEROSIL fumes silica as a Versatile Product for Solving Problems Physiological Behaviour and Industrial Safety Literature Brief List of Technical Terms Physico-Chemical Data of AEROSIL fumed silica

46 46 46 47 47 47 49 50 51 52 52 52 55 57 57 58 58 59 60 62 68

In the following we mention the registered trademark AEROSIL fumed silica sometimes as AEROSIL only with the aim of continuent scalability of tables and flow text.

1.
1.1

Silicon Dioxide, Si02

Natural Occurrences

1. Crystalline
Quartz Tridymite Cristobalite Coesite Keatite Stishovite most widespread modification, rock crystal, quartz sand forms at higher temperatures forms at higher temperatures high-pressure modification, very rare in nature modification that can be synthetically produced high-pressure modification, very rare in nature

Silicon, at 27.8 % by wt., is the second most widespread ?element after oxygen (46.6 % by wt.) found in the earths 17-km-thick crust. In nature, silicon is almost always bonded to oxygen, either to oxygen alone as SiO2 or, as in the silicates, with additional elements. Representatives of the silicates are, among others, the bentonites (for example montmorillonite (Al1.67 Mg0.33)[(OH)2/Si4O10] Na0.33 (H2O)4), talc Mg3[(OH)2/Si4O10], and wollastonite Ca3[Si3O9]. The natural silicates form the raw material base for important technical products such as cement, glass, porcelain, brick, etc. Pure silicon dioxide can occur in amorphous or crystalline form. The known modifications of SiO2, which, for the most part, occur in nature, are compiled in Table 1. With regard to quartz and tridymite, a high-temperature form also exists in each case, it is possible to distinguish between eight crystalline SiO2, modifications. With the exception of stishovite, which has a hexagonal neighbourhood of six oxygen atoms, all other modifications are built up tetragonally with four adjacent oxygen atoms. In nature, silicon dioxide influences the growth of some plants and their resistance to fungi and insects (1). Dissolved silica is also contained, for example, in drinking water or beer (originating from the barley). It is therefore ingested in considerable quantities by humans and animals with the natural food (2).

2. Amorphous
Lechatelierite natural Si02 glass, formed by melting processes resulting from a stroke of lightning Opals not pure Si02, contain water Kieselguhr result from the SiO2 content of prehistoric infu soria and diatoms, always contaminated Vitreous silica silica glass synthetically-produced, pure SiO2 glass Table 1: Modifications of SiO2

1.2 1.2.1

Synthetic Silicas Organization

Silica family tree

Silica gels

Precipitated silicas

Arc silica

Flame hydrolysis

Plasma

Vitreous silica

The silica family tree in Figure 1 gives an overview of the most important synthetic and natural products. Today, synthetic silicas are firmly rooted components or raw materials for a wide variety of high-technology products. In 1990, annual production had reached an estimated 1,000,000 tons in the western hemisphere. This number does not include flue ash and filter dusts based on SiO2 resulting from technical processes, for example the production of ferrosilicon, or from power plants. These forms of ash and dust, in contrast to the purposely-produced materials given in Table 2, are in part highly contaminated by-products. Different production processes result in SiO2 products* with different technical and applicational properties. A practical division into various groups (3, 4) is shown by Table 2. In supplement, a differentiation is also made in each case between untreated and chemically-after-treated SiO2 products.
Quartz Diatoms Amorphous Wet process Thermalpyrogenic Vitreous silica

Crystalline Natural

Amorphous Controlled synthetic Silicon dioxide Silicon

Figure 1:

Silica family tree

Overview: Synthetic SiO2 Products

1.

Themal or pyrogenic or fumed silica

Silica by flame hydrolysis Arc silica Plasma silica

2. 3.
Table 2:

Wet process silica

Precipitated silica Silica gel

Vitreous silica

Overview: Synthetic SiO2 products produced under controlled conditions

* The designation SiO2 products is used when foreign components are intentionally

present in a larger amount. This is the situation, for example, in the case of Aluminium Silicate P 820, which represents a silica purposely contaminated with Na2O and Al2O3. Degussa AG uses the term silicates for these products in contrast to silica.

1.2.2

Silicas Produced by Degussa

All SiO2, products produced by Degussa are derived synthetically under controlled conditions. All of these products are X-ray amorphous, as clearly shown by Figure 2 where AEROSIL 200 is used as an example. Consequently, all Degussa silicas belong to the group of the synthetic amorphous silicas or SAS. This designation is increasingly found in American literature. Quantitatively, the arc silica process (5-7) is in last place. Plasma processes (8-10) are of no importance technically at the present time. In contrast, the precipitated silicas and AEROSIL fumed silicas are of greatest importance. The idea and the technical development of the original AEROSIL process (flame hydrolysis, high-temperature hydrolysis) (11-15) can be traced back to the Degussa chemist H. KLOEPFER, who wanted to produce a white carbon black following the invention of the German Channel Black Process (16). In 1941, the first small-scale production was successful. Today, this pyrogenic silica is produced throughout the entire world.
16 14 12 x103

DE-PS 762723 830786 870242 873083 877891 878342 891541 893496 893497 900339 Table 3:

DE-PS 900574 910120 921784 928228 962292 974793 1003765 1004596 1023881 1034163

DE-PS 1035854 1036875 1066552 1103313 1150955 1156918 1210421 1244125 1244126 2004443 3101720

DOS 1642994 2728490 2904199 2923182 3028364 3139070 3211431 3320968 3741846

List of the German AEROSIL patents

While the AEROSIL Brochure (17) provides an insight into the most important fields of application of AEROSIL fumed silica, in addition to a general product description, this edition in the series of Technical Bulletin AEROSIL fumed silica describes the fundamentals of AEROSIL fumed silica with respect to its physico-chemical and technical application characteristics. The synthesis of the precipitated silicas (3) which are likewise produced by Degussa AG, and their characteristics are described, for example, in (18). Field of Work or Title Adhesives Adsorption Analytical methods Applications Catalysts Characterization Coatings Cosmetics Defoamers Dispersion Electrostatic charging Epoxy resins Flatting Fluoroelastomers Free flow Handling Joint-sealing compounds Pharmaceuticals Plastics Polyester resins Printing Inks Production PVC masses Reflection measurements Rheology Silicone rubber Toothpastes Toxicology Table 4: Edition Number 44 19 16 43 72 53*, 60 18, 53,68 4,49 42 33 62 27 21 73 31 28, 70 63 19,49 13 54 26,52 6, 32 41, 51 39 23 12 9,55 64, 76

AEROSIL 200 Cristobalite Vitreous silica

Intensity (abs.)

10 8 6 4 2 0 14 18 22 26 30 34 38 42 46 50 54

2 theta

Figure 2:

X-ray graphs which show the different structures of AEROSIL fumed silica on the one hand and of cristobalite on the other. Vitreous silica is also built up randomly

Degussa operates plants in the Federal Republic of Germany, in Belgium, in the USA, and in Japan. A listing of old and new AEROSIL patents is shown in Table 3. Numerous Degussa company publications help the reader to gain a quick product overview on the one hand, or in other editions present detailed information on special applications. Within this series of Technical Bulletin Pigments, the editions selected in Table 4 discuss the specialized fields mentioned.

Editions in the series of Technical Bulletin Pigments

* Not yet published in English

1.2.3

Comparison: AEROSIL/Wet Process Silicas

Some important physical characteristics of AEROSIL products and silicas produced according to wet processes are compared with each other in Table 5.

Pyrogenic or thermal silicas AEROSIL Characteristics Arc silicas Aerosols m2/g nm m g/cm % % nm ml/100 g
3

Ground wet process silicas Precipitated silicas Silica gels Silica gels Aerogels

1 Spec. surface according to BET 1) 2 Primary particle size 3 Aggregate or agglomerate size 4 Density
2)

50 to 600 5 to 50
11)

25 to 300 5 to 500 2 to 15 2.2 500 to 1000 1.5 1 4.5 not porous 100 to 150
11)

30 to 800 5 to 100 1 to 40 1.9 to 2.1 3 to 7 3 to 7 5 to 9 30 10) 175 to 320 very wide small
8)

250 to 1000 3 to 20 1 to 20 2.0 100 to 200 3 to 6 3to15 3 to 8 2 to 20 100 to 350 narrow very large

250 to 400 3 to 20 1 to 15 2.0 800 to 2000 3 to 5 3 to 5 2 to 5 25 200 to 350 narrow large

2.2 1000 to 2000 2.5 1 to3 3.6 to 4.3 not porous to 2 app. 300 m /g 250 to 350
11)

5 Compacted apparent volume 3) 6 Drying loss 4) 7 Ignition loss 5) 8 pH value 6) 9 Predominant pore diameter 10 Dibutyl phthalate adsorption 7) 11 Pore diamete distribution 12 Proportion of the internal surface 9) 13 Structure of the aggregates and agglomerates 14 Tendency to have thickening effect Table 5:
1) 2) 3) 4) 5) 6) 7) 8) 9)

ml/100 g

200 to 2000

0
chain-like agglomerates very strongly pronounced

strictly spherical mod. aggregated very highly aggl. aggl. porous part. only slightly aggl. almost spher. part. porous part. distinct indicated present present indicated present present

Overview of some important characteristics of industrially-produced silicas (compiled for the purpose of making differences recognizable) according to [3]

10) 11)

with ref. to DIN 66 131 with ref. to ISO 787/10 with ref. to ISO 787/11 with ref. to ISO 787/2 with ref. to DIN 55 921 with ref. to ISO 787/9 with ref. to DIN 53601 depending on water content estimate by comparison of BET and EM surfaces or according to practical experience in exceptional case smaller, for example SIPERNAT FK 310 (Degussa) can not be given

Distinct differentiating features exist in the aggregate or agglomerate size. All silicas produced according to wet processes are ground if they are not spray-dried. On the other hand, AEROSIL fumed silica is neither ground nor specially dried. In all cases, the smallest particles are the primary particles, which are more or less strongly aggregated and agglomerated. The specific surface is of central importance. Silica gels have a very large inner surface, which results in a high adsorption capacity. In contrast, AEROSIL fumed silica primary particles derived by flame hydrolysis have only an outer surface. This explains, for example, the improvement in the rheological characteristics of numerous systems resulting from the incorporation of AEROSIL products. On the other hand, the pronounced pore volume of silica gels is of importance for the adsorption as well as for the chromatography. As mentioned, the differences in the particle size and particle structure are reflected in the rheological characteristics. The reasons for using AEROSIL fumed silica as a reinforcing, thickening and thixotropic agent for many diverse systems become obvious. While stable AEROSIL fumed silica dispersions represent a sales product, dispersions of precipitated silicas, for example, tend to settle. Furthermore, differences in the drying and ignition losses play a major role for the characterization and for the application of the products. Low drying losses are required, for example, because of better dielectric characteristics, for cables based on silicone rubber, and for an adequate storage stability when used in one-component adhesives or coatings. The most important difference, which is not listed numerically in Table 5, has its roots in the differing silanol group density (i.e. SiOH/nm2). All hydrophilic types of AEROSIL products have values between 2 and 3. In contrast, this parameter lies at about 6 with all products derived from wet processes.

Considerable differences are also found in the purity (more detailed data for AEROSIL products in Section 3.4). In terms of anions, AEROSIL fumed silica contains only slight amounts of Cl- ( 250 ppm as HCl). Silicas produced according to the wet process usually contain sulphate and alkali or alkaline earth ions (for example ~ 1000 ppm).

1.2.4

AEROSIL Products

Table 6 shows the types of AEROSIL products and special oxides produced by Degussa available on the market. Here, a subdivision was made between untreated and chemicallyaftertreated AEROSIL. All of the latter, the hydrophobic types of AEROSIL, have an R in their nomenclature. This letter, R, is taken from the word repellent. This R should not be confused with the for registered trademark. The pyrogenic, likewise highly-dispersed special oxides, AEROXIDE Alu C, AEROXIDE TiO2 P 25 , and experimental product* Zirconium Oxide, are also included in this product group (19). Moreover, Degussa also markets a series of AERODISP, AEROSIL dispersions, the technical data of which are compiled on Page 36.
* The term experimental products (German abbreviation: VP) applies to a product which is still produced in relatively small amounts; in the case of such products, a decision has not yet been made regarding their inclusion in the production program.

1. AEROSIL

2. Chemically aftertreated AEROSIL

AEROSIL OX 50 AEROSIL 90 AEROSIL 130 AEROSIL 150 AEROSIL 200 AEROSIL 300 AEROSIL 380 AEROSIL TT 600 AEROSIL MOX 80 AEROSIL MOX 170 AEROSIL COK 84 Table 6:

AEROSIL R 972 AEROSIL R 974 AEROSIL R 202 AEROSIL R 805 AEROSIL R 812
3. Special oxides

AEROXIDE Alu C AEROXIDE TiO2 P 25

Highly-dispersed pyrogenic oxides produced by Degussa

0

2.
2.1

Production
Production of Hydrophilic AEROSIL fumed silica

Instead of silicon tetrachloride, silanes such as methyltrichlorosilane, trichlorosilane, etc. can be used as the raw material, either alone or in mixtures with SiCl4. The conditions relating to firing and flow must be varied in comparison with those used for silicon tetrachloride in order to derive the same final product.

The AEROSIL Process (11 - 15), i. e. the large-scale industrial synthesis of AEROSIL products, can be described essentially as a continuous flame hydrolysis of silicon tetrachloride (SiCl4). During this process, SiCl4 is converted to the gas phase and then reacts spontaneously and quantitatively in an oxyhydrogen flame with the intermediately-formed water to produce the desired silicon dioxide.

SiCI4
1000 C

2 H 2 + O2 SiCl4+ 2 H20 2 H2 + O2 + SiCl4

2 H2 0 Si02 + 4 HCI Si02 + 4 HCI

H2 O2
Figure 3:

SiO2
Flame sceme for AEROSIL fumed silica (schematic)

During this chemical reaction a considerable amount of heat is released, which is eliminated in a cooling line. The only byproduct is gaseous hydrogen chloride which is separated from the AEROSIL fumed silica solid matter. Figure 3 shows the flame sceme for AEROSIL fumed silica schematically; Figure 4 , a flow chart of the AEROSIL Process. By varying the concentration of the coreactants, the flame temperature, and the dwell time of the silica in the combustion chamber, it is possible to influence the particle size, the particle size distribution, the specific surface, and the surface properties of the silicas within wide boundaries. Figure 4:
Evaporator

Hydrogen Oxygen (air)

Mixing chamber

HCl adsorption

Separation

Si tetrachloride
Burner Silo

Cooling line Deacidification

Fumed Silica

Production of AEROSIL fumed silica (flow chart)



The hydrochloric acid which develops during the AEROSIL process in the tetramolar excess, referred to as SiO2 , can be used again in the production of SiHCI3 or SiCl4 according to the equation

Unlike AEROSIL fumed silica which is completely amorphous, the special oxides Al2O3C, TiO2 P 25, and the experimental product Zirconium Oxide occur in crystalline form (19). In all cases, the thermodynamically instable forms are more readily formed because the actual reaction time is extremely short. The short dwell times in the oxyhydrogen flame practically preclude sintering processes between the condensing phases which are conceivable in principle. The prerequisites for an easy and effective dispersing, which is of great applicational importance, are therefore established. In Table 8, some further experimental products are compiled

Si + 4 HCl SiCl4 + 2H2

Here, ferrosilicon (FeSi) serves as the silica source; FeSi is a product used, for example, in the production of steel. The hydrogen formed is likewise used and is fed into the burner for the production of AEROSIL fumed silica, so it is possible to speak of an environmentally-friendly, large-scale, cyclic process.

AlCl3 Al2O3
AEROXIDE Alu C

TiCl4 TiO2
AEROXIDE TiO2 P 25

ZrCl4 ZrO2
Experimental product Zirconium Oxide

which have been produced on a laboratory or pilot plant scale. The limiting factor during the production is represented by the volatility of the raw materials. The special oxides in Table 8 are either derived in pure form or are doping substances in silica or titanium dioxide carriers.
Experimental product Raw material Experimental product Raw material

Al2O3 C
Table 7:

TiO2 P 25

VP ZrO2

Special oxides produced by Degussa according to the AEROSIL process

2.2

Production of Highly-Dispersed Pyrogenic Special Oxides

AIBO3 AIPO4 BPO4 Bi2O3 Cr2O3 Fe2O3 GeO2 Table 8:

AICI3/BCI3 AICI3/PCI3 BCI3/POCI3 BiCI3 CrO2CI2 FeCI3 Fe(CO)5 GeCI4

NiO MoO3 SnO2 V205 WO3 VPZrO2

Ni (CO)4 MoCI5 SnCI4 Sn(CH3)4 VOCI3 WCI6 WOCl4 ZrCI4

The easy evaporation of SiCl4, the development of only one form of solid matter, and the use of suitable materials for apparatus inevitably result in the formation of extremely pure products. Therefore, it also seemed reasonable to extend the process to other chlorides which can likewise be converted more or less easily into the gas phase, as shown by Table 7. AEROXIDE Alu C and AEROXIDE TiO2 P 25 have long been on the market as highly-dispersed, pyrogenic oxides. Zirconium Oxide is still handled on the market as an experimental product. The characteristics of the special oxides and their applications are discussed in detail in Editions No. 56 and 72 in this series of Technical Bulletin Pigments.

List of some pyrogenic special oxides and mixed oxides which in principle can be produced according to the AEROSIL process. VP ZrO2 is an experimental product, samples can be requested. Samples of the other products are currently not available

2.3

Chemical After-treatment

If AEROSIL fumed silica is mentioned today, AEROSIL hydrophobic* products are often also included. Here, the AEROSIL process described above is followed by an additional stage the aftertreatment.

* Hydrophobic = water repellent; for more detailed information, see

also 3.6.4, the measurement of the hydrophobicity is discussed in detail in Edition 18 - among other sources in this series of Technical Bulletin Pigments.



Silicon tetrachloride
Flame Hydrogen + oxygen

The functionalization of the AEROSIL fumed silica surface is carried out with halogen silanes, alkoxysilanes, silazanes,
SiOH R H Y R R2
Transmittance %

siloxanes, etc. Figure 7 compares the surface groups of the

2

AEROSIL + hydrochloric acid Silane

commercial hydrophobic types of AEROSIL fumed silica.

100 80 60 40 20 0 100 80 60 40 20 0 3500 3000 2500 4000 3500 3000 2500

Si Y R3

(Aftertreatment)

AEROSIL 300

AEROSIL R 812

Hydrophobic prod. AEROSIL

Figure 5:

Si O Si R R3

The direct aftertreatment, integrated into the fully continuous AEROSIL process (schematic)

When the material is still, so-to-speak in statu nascendi, i. e. it has not yet left the system, it is especially reactive for a further treatment with a silane. The direct aftertreatment (Figure 5), which is integrated into a continuous process, results in homogeneous and effective functionalization. This applies for every modified silica for special applications just as for the hydrophobic standard products. By means of the infrared spectra, the reaction processes can be observed well. Figure 6 shows that during the chemical aftertreatment, and essentially in the case of the hydrophilic AEROSIL fumed silica, the sharp band of the free silanol groups at 3748 cm disappears from the IR spectra. Simultaneously, a
-1

4000

Wave number cm-1

Figure 6:

Partial IR spectrum of AEROSIL 300 (left) before and after the chemical aftertreatment (right, corresponds to AEROSIL R 812); in each case pure substance test specimen, IR instrument: Perkin Elmer 325

AEROSIL R 972 AEROSIL R 974

AEROSIL R 812

O O O

Si

CH3 CH3

Si

new C-H oscillation band of the methyl groups is observed at less than 3000 cm-1 with the final product. The silanol groups are irreversibly replaced in a chemical reaction by organic residues such as, for example, methyl groups.

CH3 CH3 CH3

AEROSIL R 805

AEROSIL R 202

O Si C8H17 O
Figure 7:

CH3 ( Si O ) n CH3

Hydrophobic types of AEROSIL fumed silica



AEROSIL hydrophobic types differ from the hydrophilic starting silicas by a among other things - lower silanol group density, and therefore a - lower water vapor adsorption. For this reason, the aftertreated silicas have new, technicallyimportant applicational properties. For example, as represented in Figure 8, the maximum moisture adsorbed by a hydrophobic silica is distinctly less than that adsorbed by a hydrophilic type. In addition, Figure 9 where a selected example of the thickening effect is used for illustration shows the advantage of an AEROSIL hydrophobic type in a low-viscosity, reactive epoxy resin before and after the addition of a mixture composed of a polyamino amide as cross-linking agent and a tertiary amine as accelerator. The hydrophobic types, AEROSIL R 202 and
Viscosity Pa s Moisture adsorption in %

10 8 6 4 2

AEROSIL 150

AEROSIL R 202
0 0 20 40 60 80 100

Relative atmospheric moisture %

Figure 8:

Water vapour adsorption isotherms at room temperature of AEROSIL 150 (hydrophilic starting material) and the hydrophobic AEROSIL R 202, measured on small test specimens
without with hardener

400

160
AEROSIL 300 AEROSIL R 202

300

AEROSIL R 805

120

AEROSIL R 805, are distinctly superior to AEROSIL 300 in the epoxy resin; for additional details, see Edition No. 27 in this series of Technical Bulletin AEROSIL.

200

80

100

40

15

30

45

0 60

Time after addition of hardener, min.

Figure 9:

Change in viscosity of an epoxy resin (ARALDIT M, Vantico AG) with 5.6 % AEROSIL before and 3.8 % AEROSIL after addition of the hardener and crosslinking agent (EUREDUR 250, Schering AG; ARALDIT hardener HY 960). As a result of this addition, the AEROSIL content decreases



Viscosity Pa s

3.
3.1

Characteristics
Amorphous Structure and Thermostability

As already shown, the chemical summation formula of AEROSIL fumed silica is SiO2. However, it must be taken into consideration here that in reality no isolated SiO2 molecules are present. Instead, the silicon atoms develop covalent single bonds with four directly adjacent oxygen atoms. Figure 10: Consequently, every atom corresponds to the octet rule. For energetic reasons, the bonding electron pairs occupy positions as far from each other as possible; in other words they are arranged tetrahedrally. The SiO4 tetrahedrons serve as the fundamental building blocks for the structure of the macromolecular network. In principle, two possibilities are conceivable here: the SiO4 tetrahedrons could be arranged regularly, or they could be arranged completely at random. In their entirety, crystalline modifications of silica that occur in nature such as quartz, tridymite, or cristobalite consist of exactly defined, fully identical structural units, the so-called unit cells. Due to the regular structure of the crystral lattice, X-rays are diffraced at the lattice or net planes, and exhibit interference phenomena. All synthetic silicas produced by Degussa display an entirely different behaviour. The SiO4, tetrahedrons are randomly arranged, as Figure 10 shows by the absence of defined diffraction rings or lines. This fact was already noted in Figure 2. AEROSIL fumed silica is therefore X-ray amorphous. In contrast to glasses, which form a three-dimensional skeleton with infinite expansion (measured in atomic dimensions), AEROSIL amorphous silica has a particular structure. X-ray photographs of AEROSIL fumed silica (above), -cristohalite (centre), and quartz (below); compare Figures 2 and 12



AEROSIL fumed silica does not produce any sharp X-ray reflections, but instead only weak, very diffuse intensity modulations. These diffraction phenomena are entirely compatible with a random network model (20). They must be attributed to short-range order conditions, the range of which in non-crystalline materials is always small in comparison with the particle size of highly-dispersed materials. In vitreous silicas, these lie in the order of magnitude of about 1.3 nm, in precipitated silicas at about 1.2 to 1.0 nm, and in AEROSIL fumed silica and arc silicas at about 0.9 and 0.8 nm (21). The transition from a regular condition to a random condition therefore takes place as early as after the third tetrahedron coordination sphere. With regard to this short-range order tendency, AEROSIL fumed silica has the greatest structural disorder in comparison with other Si02 products (21). It should be expressly emphasized here that the shortrange order regions must not be equated with a state of crystallinity. Figure 11: Schematic arrangement of the SiO4 tetrahedrons in AEROSIL according to a model by EVANS and KING (22). The circles symbolize oxygen atoms; in the centers of the tetrahedrons are the silicon atoms



According to EVANS and KING (22), it is possible to imagine the SiO4 network as shown in Figure 11. By calculating the radial distribution function, a Si-O distance of 0.152 nm and a Si-Si distance of 0.312 nm were determined. The Si-O-Si bond angle
Intensity l rel.

has a considerable range of variation of 120-180 degrees (23). Quartz dust especially, and dusts containing cristobalite, tridymite, and coesite have a silicogenic effect (24, 25). The amorphous structure of AEROSIL fumed silica is especially significant. The question of possible silicotic effects linked to amorphous silica is discussed specifically in Edition No. 76 in this series of Technical Bulletin Pigments (26). It has not been possible to observe crystalline components in AEROSIL fumed silica test specimens by IR spectroscopy, with the aid of differential thermal analysis, or by means of X-ray diffraction. This can be recognized clearly in Figure 12. The roentgenographic detection limit of moderately disordered cristobalite in vitreous silica lies below 0.3 % cristobalite (27).

AEROSIL 200 + 2% quartz

AEROSIL 200 + 1% quartz AEROSIL 200 + 0.5% quartz

AEROSIL 200 + 0.3% quartz AEROSIL 200

25.5

27.5

2 x theta

Figure 12:

Angle region of the [101] reflection from -quartz, represented with AEROSIL 200 / -quartz, mixtures. AEROSIL 200 itself shows no reflection, it is therefore X-ray amorphous. Diffractometer STADI 2/PL STOE, CuK1 radiation, 50 kV 28 mA. Measurement stimulus per step 30 seconds (also see Edition 64 in this series of Technical Bulletin AEROSIL fumed silica on this subject)



When heated to temperatures of up to 1000 C (7 days, purest conditions), AEROSIL fumed silica does not change its morphology according to scanning electron microscope findings. The large half width of the first X-ray diffraction maximum receeds somewhat during the thermal loading. The slight increase in order corresponding with this is still in agreement with a completely amorphous network. At 1200 C, AEROSIL pulverulent silica cross-links to glass, whereby with a longer annealing time devitrification takes place. As expected, the recrystallization behaviour is greatly influenced by additives. Figure 13 shows how the stability of AEROSIL 300 can be increased by adding ZrO2. AEROSIL R 974 shows a behavior analogous to that of AEROSIL 200 during the annealing. When the methyl groups are burned off (above 500 C), the crystallization behaviour is therefore not influenced. For practical purposes, the temperature stability of hydrophilic AEROSIL fumed silica lies at 850 C according to Table 9 (continuous stability). Regarding the recrystallization rate, precipitated silicas differ considerably from AEROSIL. While the pyrogenic silica is still present in an amorphous state even after 7 days at 1000 C, standard precipitated silicas are completely crystallized after only 20 minutes at the same temperature (21). In storage heaters, for example, AEROSIL fumed silica is used in large amounts for the insulation. Figure 14 shows insulation plates on an AEROSIL fumed silica base for the enclosing of aircraft turbines. Figure 14: Flexible insulation packing based on AEROSIL fumed silica Figure 13: Transmission electron micrographs (TEMs); from left to right; AEROSIL 300 annealed at 1000 C, AEROSIL 300 annealed at 1150 C, AEROSIL 300 annealed at 1150 C doped with 0.2 % ZrO2 according to (28); annealing time at each temperature 3 hours



3.2

Particle Fineness and Surface

The amorphous structure of AEROSIL fumed silica and the random arrangement of the SiO4 tetrahedrons were described in 3.1. Now, the macroscopic extension and form of the particle will be discussed. Visually, AEROSIL fumed silica is identified as a loose, bluish-white powder. Actually, AEROSIL fumed silica consists of about 98 % by vol. of air (density of AEROSIL 2.2 g/cm3, tapped density of AEROSIL normal product about 50 g/l; compressed product V about 120 g/l). It can be easily fluidized with bursts of compressed air, and consequently can also be handled in silos with no problems. Figure 15 illustrates this behavior using a simple laboratory demonstration.

Figure 15:

Simple laboratory demonstration of the fluidizing of AEROSIL fumed silica; compressed air is applied to the glass frit at a pressure of about 0.2 bar



With the eye, it is possible to recognize very small AEROSIL fumed silica particles as well as larger, loose network structures which collapse when touched even lightly. Micrographs of AEROSIL fumed silica dust particles show that agglomerates of about 10 to 200 m form, whereby the frequency of one group of 10 to 30 m and a second of about 100 m stand out (29). We may conclude from these data that a large portion of the AEROSIL fumed silica dust must not be included in the fine dust able to enter the alveoli, see (30). Figure 16: Definition of the terms primary particles, aggregates, and agglomerates according to DIN 53 206, Sheet 1 (August 1972)

The dust-free handling of AEROSIL products in general and also the conveying in pipelines are standard practice nowadays (31). Interested customers can convince themselves of the simple and correct handling of AEROSIL products in a Degussa pilot plant at our location in Wolfgang or Mobile. In order to be able to describe the conditions prevailing with AEROSIL fumed silica more effectively, the terms: primary particles, aggregates, and agglomerates are initially defined in Figure 16.

Hexahedral

Spherical

Rod shaped

Irregularly shaped

Primary particles: smallest recognizable individuals

Coherent

Dispersive

Lattice regions

(Crystallites)

Aggregates: primary particles contacting each other at surfaces or edges; as a rule, can not be broken down further

Agglomerates: aggregates and/or primary particles contacting each other at points

0

3.2.1

Particle Size and Structure

The AEROSIL fumed silica primary particles are extremely small; the order of magnitude lies in the range of just a few nanometres, and therefore is hardly conceivable. An imaginary experiment will be described to illustrate this: if it were possible to blow up a normal football (soccer ball) to the size of our planet earth, then an AEROSIL fumed silica primary particle, under the same conditions, would be about the size of the football. Nevertheless, an AEROSIL fumed silica primary particle is built up of about 10,000 SiO2 units because, as mentioned in 3.1, the Si-Si distance is only about 0.31 nm (32). Figure 17: TEM of AEROSIL OX 50

Figure 18:

TEM of AEROSIL 130



Due to the particle fineness, electron microscopy is the only direct method to determine the form and size of the particles. Transmission electron microscopy (also abbreviated TEM) offers outstanding resolution ( 0.2 nm, magnification up to about 2,000,000:1), but provides only a two-dimensional impression. Spherical particles therefore appear as round discs. Details on this are given in Edition No. 60 in this series of Technical Bulletin Pigments.

Figure 19:

TEM of AEROSIL 200

Figure 20:

TEM of AEROSIL 380



Important items of information can be derived from the TEMs:

30 25

Frequency [%]

. . . . .

AEROSIL fumed silica is built up of many almost spherical primary particles. The primary particles form a loose network; they occur practically non-isolated (the only exception is in part with AEROSIL OX 50). The smaller the primary particles, the more strongly pronounced the aggregate/agglomerate formation. Especially Figure 20 shows that the AEROSIL fumed silica primary particles often line up with each other, forming irregular chains. One type of AEROSIL fumed silica shows primary particles with a particle size distribution. The individual types of AEROSIL fumed silica differ distinctly in the primary particle size: the average primary particle size ranges from 7 to 40 nm depending on type. Figure 21:
20 15 10 5 0

AEROSIL 300 AEROSIL 200 AEROSIL 130 AEROSIL 90 AEROSIL OX 50

20

40

60

80

100

Particle diameter [nm]

Primary particle size distribution curves of various types of AEROSIL fumed silicas. Here it must be considered that the frequency depends on the class width; AEROSIL 380 and AEROSIL 300 have almost identical distribution curves

The particle size distribution in the individual types of AEROSIL fumed silica is represented in Figure 21. In this connection, it can be noted that AEROSIL types with a high BET surface have very narrow ranges of fluctuation in the size distribution. According to SEIBOLD and VOLL, this fact can be explained by means of empirical distribution functions (33).



From the point of view of technical applications, the dispersibility of AEROSIL fumed silicas is of decisive importance in most cases. Due to the greater aggregation or agglomeration, the dispersibility is naturally more difficult when smaller primary particles are present. For example, AEROSIL 130 can be dispersed more easily than AEROSIL 200, and the latter in turn more easily than AEROSIL 300. Furthermore, AEROSIL hydrophobic silica offers distinct advantages over AEROSIL hydrophilic silica with regard to the dispersibility. This fact is represented in Figure 22. The TEM`s show that the network structure, for example in the case of AEROSIL R 972, is less pronounced than in the hydrophilic base material, AEROSIL 130.

Figure 22:

TEMs of AEROSIL 130 (above, hydrophilic starting material) and AEROSIL R 972 (below)



Figure 23 shows that the transparency of comparable HTV silicone rubber test samples containing AEROSIL fumed silica
Transparency scale divisions

30 25 20 15 10 5 0

AEROSIL hydrophilic silica

AEROSIL hydrophobic silica

decreases, for example, in the following order:

AEROSIL R 812 AEROSIL 300 AEROSIL 200 AEROSIL 130.

In the same direction, the size of the AEROSIL fumed silica particles effectively present increases with these samples. Evidently, the dispersing energy during the production of the corresponding samples was adequate to disperse AEROSIL 200 and AEROSIL 300 to a large extent, too. Since AEROSIL R 812 and AEROSIL 300 have about the same average primary particle size, the further rise in the transparency when AEROSIL R 812 is used must be explained by the easy dispersibility of hydrophobic AEROSIL products and its better wettability. Scanning electron microscopy (SEM), with its resolution of about 5 nm, is inferior to the TEM technique, but offers the advantage of a great depth of focus. As can be recognized in Figures 24 and 25, realistic, three-dimensional pictures are derived which provide further information about the structure of AEROSIL products. Regardless of the primary particle size, snowballs of about 100 nm in size can be observed in AEROSIL OX 50 and AEROSIL 200. These snowballs make quite a compact impression; during dispersion, they cannot be completely broken down into smaller particles. With the SEM technique, therefore, primary particles can not be made visible.

AEROSIL 130

AEROSIL 200

AEROSIL 300 AEROSIL R 812

Figure 23:

Influence of the particle size and the hydrophobicity of AEROSIL fumed silica on the transparency of HTV silicone rubber (100 parts polymer, 40 parts AEROSIL, 0.5 % peroxide)

AEROSIL 0X 50

d = 40 nm
Figure 24: SEM of AEROSIL OX 50 (see text). Left, ad-jacent, greatly enlarged, an AEROSIL OX 50 primary particle of average size; this makes a comparison of size possible between the primary particles (AEROSIL 200 in Figure 25)



In the sense of the definition in Figure 16, therefore, we speak of aggregates. These structures develop through the clustering together of primary particles. The standard practice of coating the particular study objects with a gold layer of about 5 nm in thickness used with the SEM technique also has the effect of smoothing the surface in the case of AEROSIL fumed silica. The SEMs permit very good recognition of the agglomerate structure. The smaller the primary particle size, the more pronounced this structure is. During the breakdown of the agglomerates to aggregate size, distinctly more dispersive force must therefore be exerted in the case of AEROSIL 200 than in the case of AEROSIL OX 50. This also applies for all other types, for example for AEROSIL 300, which in turn is more difficult to disperse than AEROSIL 200. SEMs of frozen cross sections of AEROSIL dispersions show that the secondary particle size (aggregates) effectively present actually lies in the 100-nm range. This is also confirmed by results of different particle sizing techniques, as shown by Figure 26. Such dispersions are available in the AERODISP product range (see page 35).
Particle Size Distribution (Volume)
350

AEROSIL 200

d = 12 nm
Figure 25: SEM of AEROSIL 200 (see text). On the left, greatly enlarged, an AEROSIL 200 primary particle of medium size; this permits a comparison to be made of the primary particle size (AEROSIL OX 50 in Figure 24)

According to DIN 53 601, it is common practice to determine a so-called dibutyl phthalate adsorption on finely divided materials. This value essentially describes the so-called void volume. Naturally, the size of the specific surface also influences this numerical value, as shown by Figure 27.

35 30 25

q3 (%)

q3 (%)

20 15 10 5 0 0.01 0.10 1.00

Size [m]

100 90 80 70 60 50 40 30 20 10 0 10.00

300 250

DBP adsorption [g/100g]

200 150 100 50 0 0 200 300 400

100

BET surface [m /g]

Figure 26:

Particle size distribution in AERODISP W 7520 measured using static light scattering (Horiba LA-910)

Figure 27:

Dibutyl phthalate adsorption of AEROSIL fumed silica (DBP adsorption) as a function of the specific surface (according to DIN 53 601)



3.2.2

Specific Surface

It has already been shown how the primary particle size and structure of the AEROSIL fumed silica particles can be observed from electron micrographs. In the case of the AEROSIL product types, the correlation between the primary particle size and magnitude of the specific surface can be determined by two methods that are completely independent of each other. Both methods lead to the same result.

3.2.2.1 Geometrical Determination of the Specific Surface

Figure 29:

30 g AEROSIL 200 have the same surface area as a football (soccer) field with the internationally-standardized dimensions

The fundamental correlation between the primary particle size and the specific surface can be derived quantitatively from the TEMs by mathematical methods (34). In this method of determination, several thousand particles are counted with a ZEISS Particle Size Counter TGZ 3 according to ENDTER and GEBAUER (35), and the specific surface is calculated. Figure 28 shows how the specific surface sharply increases as the particle diameter decreases. 30 g of AEROSIL fumed silica, for example, have the same surface area as a football field. (Figure 29). The following imaginary experiment is presented to point out the significance of the finely divided nature:

If a, cube is divided into 8 small cubes when each edge length is cut in half, the mass naturally remains constant; the surface area of a single small cube is smaller, but the sum of the surface areas of the 8 small cubes is twice as large as the surface area of the large cube. This process can be repeated in the imagination as often as desired. The surface area of a single AEROSIL fumed silica primary particle is very small; on the other hand, the specific surface is very large because the number of particles is very high. If it were possible to line up the primary particles in 1 g of AEROSIL 200 to form a chain, the length of this chain would be 17 times the distance from the earth to the moon!

400

300

Spec. surface [m /g]

200

100

Average diameter of the primary particles [nm]

10

20

30

40

50

Figure 28:

Specific surface as a function, of the average AEROSIL fumed silica primary particle diameter



3.2.2.2 Determination of the Specific Surface by Adsorption

In addition to electron microscopy, the physical adsorption of gases, especially nitrogen, is the most reliable method used to determine the specific surface of highly dispersed materials. The N2 adsorption isotherms, measured at 196 C, are evaluated according to BRUNAUER, EMMETT and TELLER (BET surface) (36) and according to the t-curve method developed by DE BOER (37). The BET and the calculated TEM surfaces are found to correspond well with each other. AEROSIL 380 is an exception here. In comparison with AEROSIL 300, the particles do not become finer, but instead show a certain surface roughness. All other types of AEROSIL fumed silica, therefore, have primary particles with a smooth and nonporous surface. On the other hand, a notable porosity can be determined with precipitated silicas (38). In contrast, silica gels which are used amongst other things as flatting agents have pore volumes, 90 % of which must be classed as mesopore volumes (39); this subject is also discussed in brochure No. 32 in this series of Technical Bulletin Pigments.

After reaching the monolayer, the N2 adsorption isotherms proceed in a very flat condition, and therefore display an anomalous behaviour in comparison with other gases such as Ar, CO, and O2 (40). In addition to the VAN DER WAAL interaction, the dipolequadrupole interaction between the N2 molecule and the silanol groups apparently plays a decisive role. This interaction should only be possible, however, when a relatively opensurface structure permits an approach of the N2 molecule to the OH group.



3.3

Special Physico-Chemical Data

Refractive index Solubility in water (pH 7, 25 C) (38) Specific weight 1) Thermal capacity Cp of AEROSIL 200 Wetting heat of water on AEROSIL 200 Molar adsorption coefficient for free silanol groups (3750 cm-1) (61) Temperature stability of AEROSIL hydrophilic types Ignition temperature of AEROSIL hydrophobic types according to DIN 51794 2) Stability

1.46 150 mg/l 2.2 g/cm3 10 C: 0.79 J/g K 50 C: 0.85 J/g K -150 x 10 -7 J/m2 (4.4 0.4) x 105 cm2/mol 850 C AEROSIL R 974: 530 C AEROSIL R 805: 480 C AEROSIL R 812: 460 C AEROSIL R 202: 440 C

For technical interests, the following quantities are often relevant:

- specific surface according to BET (DIN 66 131) - average size of the primary particles - tapped density (DIN ISO 787/11) - drying loss (DIN ISO 787/2) - ignition loss (DIN 55 921) - pH value (DIN ISO 787/9) - foreign oxides - chlorine content and - sieve residue according to Mocker (ISO 787/18)
While the corresponding analytical study methods are described in (41), the physicochemical data are compiled at the end of this publication. The high temperature stability of AEROSIL hydrophilic silica (up to 850 C under continuous load) is of importance, for example, when AEROSIL fumed silica is used for thermal insulation, also see Section 3.1 on this point.

with respect to acids with respect to ammonia 5 % with respect to sodium hydroxide solution 5% with respect to oxidizing agents with respect to reducing agents Table 9:

excellent 3) slight very slight excellent excellent

Special physico-chemical data relating to AEROSIL products

density of a moduled object, air comparison pycnometer, helium AEROSIL hydrophilic silica can naturally not be brought to ignition 3) with the exception of hydrofluoric acid
1) 2)

In comparison with the hydrophilic AEROSIL fumed silica, the hydrophobic AEROSIL products have a lower temperature stability because of their carbon content (see Table 9). However, for example in the case of AEROSIL R 972, no volatile organic compounds are detected during a headspace analysis after 2 hours at 100 C with the GC/MS coupling. For purposes of supplementation, Table 9 presents special characteristics. Although quartz is considered as being practically insoluble in water at room temperature (42), it actually dissolves by about 0.015 % at room temperature and a pH of 7. This statement also applies for all AEROSIL hydrophilic types in the equilibrium state. However, the dynamics of the dissolving process differ greatly while quartz only reaches the equilibrium value after long contact times, types of AEROSIL fumed silica quickly form supersaturated solutions because of their finely divided nature and their amorphous character.

3.3.1

Solubility



250 200 150

AEROSIL 380 AEROSIL 200

20 C

3.3.2

Thermal Conductivity

A report is presented in (43) on studies relating to the spectral transfer of radiant heat at AEROSIL 380. The absolute thermal conductivity of some AEROSIL fumed silica types is represented in Figure 32 as a function of the average temperature of the heat transfer. Figure 33 compares the thermal conductivity of AEROSIL 200 with that of Degussa precipitated silica SIPERNAT 320 DS. In this comparison it must be noted that AEROSIL 200 was studied as a press plate with the densities given, while SIPERNAT 320 DS was measured in an Al foil under vacuum with higher densities.

mg SiO2 /l

MOX 170

100

50

MOX 80

10

15

20

25

Time [d]

Figure 30:

Solubility of various types of AEROSIL fumed silica in water at 20 C as a function of the contact time

120 100 0.5

Absolute thermal conductivity W/(m x K)

80

0.4

Tubidity scale division

0.5 hours
60 40 20 0

AEROSIL 300 AEROSIL 200 AEROSIL 130 AEROSIL OX 50

0.3

2 hours

0.2

24 hours
7 8 9 10 11 12 13 14

0.1

pH value

100

200

300

400

500

600

Figure 31:

Solubility of AEROSIL 200 in sodium hydroxide solution, turbidity after various standing times, 1 % aqueous dispersion

Pressing density 200 g/l

Average temperature C

Figure 32:

Absolute thermal conductivity of some AEROSIL fumed silica types, pressing density 200 g/l
AEROSIL 200 SIPERNAT 320 DS
sealed in Al foil, pressure < 1 mbar)

Figure 30 shows the solubility of various types of AEROSIL

Thermal conductivity mW/(m x K)

fumed silica. With rising alkalinity, a silicate formation advances rapidly with AEROSIL types. As clearly shown by Figure 31, this process is already quite noticeable at pH ~ 10.

12 10 8 6 4 2 0

120 g/l

150 g/l

220 g/l

250 g/l

Figure 33:

Comparison of the thermal conductivity of AEROSIL 200 (simple moulding) with the Degussa precipitated silica SIPERNAT 320 DS (sealed in Al foil, pressure 1 mbar)

0

3.3.3

Nuclear Magnetic Resonance Spectroscopy Behaviour

CH3
O Si CH2 R M1

CH3
O Si CH2 R D1

OH
O Si CH2 R T1

The 29Si atomic nuclei represent suitable probes for the more detailed characterization of hydrophilic and above all of aftertreated AEROSIL products. For example, a clear differentiation between dimethylsilyl groups and monome-thylsilyl groups is possible on the basis of the Si-CP-MAS solid state NMR
29

CH3 CH3
O Si CH3 M2

OH CH3
O Si CH2 R D2

OH OR
O Si CH2 R T1

CH3
O

OR CH3 CH2 R
O D3 O

OR CH2 R OH(R)

Si O

Si

T2

spectra with the chemical shifts. Table 10 shows SiR4 groups which can be distinguished from each other by NMR spectroscopy. At the same time, the nomenclature of these groups commonly used in literature is also given. The corresponding chemical shifts (29Si) are compiled in Table 11. Moreover, with nuclear resonance spectroscopy it was possible to show unequivocally that dimethylsiloxane chains, such as those which occur in AEROSIL R 202, are bonded chemically to the SiO2 surface. In addition to these chains, smaller cyclodimethylsiloxane rings also play a role (44). Table 10:

CH3 O Si CH2 R O O Si CH2 R CH3

D4

CH3 CH3 O Si O Si CH2 R CH2R OH(R)

D4

OH(R) O Si CH2 R O O Si CH2 R O O Si CH R 2 O C H2R (R)OH Si O O O Si O C H2R T4

T3 T4 T4

OH(R) Si CH2 R T3 O Si CH2 R OH(R)

Groups detectable by NMR spectroscopy on a silica surface after the reaction with a) monochlorosilane (M), b) dichlorosilane (D), and c) trichlorosilane (T), R = n-alkyl, R = CH3, D4, T3 , and T4 are groups arranged parallel to the SiO2 surface, while D4 , T 3 , and T4 are groups arranged perpendicular to the SiO2 surface (45)

Typ of Structure Q2 Q3 Q4 D1 D2 D3 D4 + D4 T1 T1 T2 T3 + T3 T4 + T4

Si - 91 - 101 - 110 -4 - 7.2 - 10 - 14 to -21 - 46 - 50 - 55.5 R CH3 - 59.0 R CH3 - 64 to -70

Table 11: NMR chemical shifts of silane peaks in ppm rel. liquid Me4Si (see Table 10 for the assignment). The nomenclature T2 and T3 differentiates between an Si atom with two (-O-Si-O)n units as neighbours (T2 ,) and an Si atom with one (-O-Si-O-)n and one (-O-Si-R) unit as neighbour (T3 ) corresponding to the different chem.environments, T2 and T3 also differ in the chemical shifts (46 - 48)



3.3.4

Tribo-Electricity

150 100

Specific charge C/g

characteristics are important. In Figure 34, the specific charge values (q/m values, charge/mass ratio) are compared for some products. As this figure shows, by means of suitable aftertreatment positively chargeable powder can also be produced. Zeta potentials, which likewise permit conclusion on surface charges, will be discussed in Section 3.6.3.4.

50 0

VP R 504*

For some applications, for example toners, the tribo-electric

TiO2 P 25 TiO2 T 805

**

Al2O3C VP ZrO2

-100 -150 -200

3.3.5

Refractive Index

Figure 34:

AEROSIL 200

The refractive indices of the individual AEROSIL types only differ from each other insignificantly. In order to determine these indices, the AEROSIL samples are suspended in carbon tetrachloride. By means of the turbidity-temperature curve, the turbidity minimum is ascertained. When this method is employed, the refractive index of carbon tetrachloride at the lowest turbidity corresponds to that of the hydrophilic AEROSIL types. At 1.45, AEROSIL R 202 has the lowest value.

Specific charge measurement (C/g) on pyrogenic Degussa oxides. Measuring instrument: Epping GmbH, carrier: C 1018, 1 % * chemically aftertreated AEROSIL 200, VP R 504 ** chemically aftertreated TiO2 P 25, TiO2 T 805

The Degussa product AEROSIL 200 Pharma is intended specifically for the pharmaceutical industry, having been tested in accordance with the Pharmacopoeia European and the United States Pharmacopoeia National Formulary (Ph. Eur. and USP/NF) and being supplied with a corresponding certificate of analysis.

3.4

Purity

In the production of AEROSIL fumed silica, highly volatile silicon compounds serve as educts, which are reprocessed by distillation and therefore are used in pure form (see Section 2). During the flame hydrolysis, the only by product that develops is gaseous hydrogen chloride, which can be almost entirely separated from the solid matter. The result is a product of high purity. For example, the SiO2 content in AEROSIL fumed silica is greater than 99.8 %. AEROSIL 200, meets the requirements of monographs contained in numerous pharmacopoeias and official specifications (Table 12).

European Pharmacopoeia (Ph. Eur.) US Pharmacopoeia/National Formulary (USP/NF) Deutsches Arzneibuch (DAB) British Pharmacopoeia (BP) Pharmacopoeia of Japan (JP)
Table 12:

Silica, colloidal anhydrous Colloidal silicon dioxide Hochdisperses Siliciumdioxide Colloidal anhydrous silica Light anhydrous silica acid

Principal pharmacopoeia monographs for fumed silicon dioxide



AEROSIL R 972

AEROSIL R 202

-50

Among the impurities (which all together make up a maximum of 0.2 %), above all Al2O3, Fe2O3, and TiO2 are of importance. Additional foreign elements occur only in traces, as shown by Table 13. A comparison with precipitated silicas is given in Table 14.

3.5

Oxide Mixture and Mixed Oxides

In order to derive products with other characteristics, synthetic silicas are treated with Al compounds. Some AEROSIL fumed silica types (for example, AEROSIL COK 84, AEROSIL MOX 80, AEROSIL MOX 170) contain defined amounts of aluminium oxide. The desired dosage can be carried out in two different

Element content
0.01 ppm As Au Sc Th U 0.1 ppm Cd Co Mo Pb Sb 1 ppm Cr Cu Hg In K Mg Mn 10 ppm Al Ba Ca Fe Na Ni Sn Zn

ways, which in part lead to products with different applications. The difference between an oxide mixture and a mixed oxide is shown by Figure 35.

Table 13:

Trace element impurities in AEROSIL 200 and AEROSIL OX 50. The limits given contain mean values from arbitrarily-selected samples, but do not represent any specifications. Study method: neutron activation analysis or AAS, total content SiO2 (%) 98.0 99.8 Impurities (ppm) 20,000 2,000 Figure 35:

SiO2 Al2O3

Product

SiO2 doped with Al2O3 (Si-O-Al-O-Si)

Precipitated silica AEROSIL

Table 14:

Schematic comparison of an oxide mixture (left: AEROSIL COK 84) with a mixed oxide (right: AEROSIL MOX 80 or AEROSIL MOX 170)

Comparison of the SiO2 content and the total impurities



3.5.1

AEROSIL COK 84

20

By mechanically mixing about 84 % AEROSIL 200 and about 16 % AEROXIDE Alu C, an oxide mixture develops which is
Viscosity Pa s

15

AEROSIL COK 84

known as AEROSIL COK 84. The primary particles here consist of either SiO2 or pure Al2O3. AEROSIL COK 84 has proven successful in the thickening and thixotropizing of pure, polar liquids. The term polar in this connection is intended to mean that the molecules in the liquid are able to form hydrogen bridge linkages. Figure 36 shows that water is thickened distinctly better with AEROSIL COK 84 than with AEROSIL 200. However, this statement can not be applied, to dispersions of plastics because the composition of AEROSIL COK 84 is optimized for water without emulsified polymers, etc. In other systems, it is quite possible that the best thickening effects are to be achived with other AEROSIL 200-

10

AEROSIL 200
0 0 1 2 3 4 5

AEROSIL concentration %

Figure 36:

Thickening effect of AEROSIL 200 and AEROSIL COK 84 in water

6000

Water
4000

Isopropanol

Viscosity m Pa s

AEROXIDE Alu C mixtures (see Figure 37). In order to explain the thickening and thixotropic effects of AEROSIL COK 84 in polar liquids, we need to discuss the formation of a spacial, or three-dimensional network as a model. Since the silica becomes charged negatively due to the dissociation of the acidic silanol groups in contrast to the AEROXIDE Alu C, the interaction with the positive aluminium oxide particles is supported by the different electrostatic charge.

2000

Dimethyl formamide

20
AEROSIL 200 %

40 60

60 40

100

80

Aluminium Oxide C %

80 20

100 0

Figure 37:

Thickening of polar liquids with 3 % of an AEROSIL 200 / AEROXIDE Alu C mixture



AERODISP fumed silica dispersions W 7520 Appearance Solid-Content pH value 2) Viscosity at 20 C 3) Density (20 C) Container Weight (net) Table 15:
mPa . s g/cm3 kg
1)

W 7622 W 1226 W 1714 W 1824 W 1836 W 7215 S W 7512 S WK 3415) G 12204) milky-white liquid 22 1000 1.13 26 9 - 10 100 1.16 14 5-6 100 1.08 24 5-6 150 1.15 34 4-6 200 1.23 15 5-6 100 1.09 12 5-6 100 1.07 41 2.5 - 4 1000 1.28 20 300 1.23

wt %

20 100 1.12

9.5 - 10.5 9.5 - 10.5

(60 kg canister, 220 kg drum or 1000 kg IBC)

These are non-binding guide values.

Technical data of a selection of AERODISP fumed silica dispersions

1) 2) 3) 4) 5)

Solid contents may vary +/- 1 % Measured according to EN ISO 787-9 method Measured according to DIN EN ISO 3219 at a shear rate of 100 s-1 Dispersion Medium is ethylene glycol Silica surface is recharged to a cationic (positive) surface charge

In comparison with some organically modified, layer-type silicates, AEROSIL COK 84 offers the following advantages when used in aqueous systems:

3.5.3

AERODISP fumed silica dispersions

Degussa provides various dispersions for many different applications. They are manufactured using innovative technologies and are known under the AERODISP trademark. They are either based on water or ethylene glycol and contain our fumed silicas (AEROSIL) or fumed metal oxides (AEROXIDE). Our product portfolio includes dispersions with different pH values and solid contents to satisfy a wide range of requirements. AERODISP dispersions are easy to handle and work with. In many applications their properties outperform those of powders.

- no masterbatch necessary - later increase in viscosity poses no problems - viscosity is only slightly sensitive to electrolytes - viscosity is relatively temperature-stable - so reactive organic components - pure white powder.

3.5.2

AEROSIL MOX 80 and AEROSIL MOX 170

Our AERODISP dispersions have a milky-white appearance and low viscosity.Depending on the product, solid contents are between 12 to 50 % by weight with narrow particle size distributions ranging from 50 to 300 nm.The dispersing processes, as well as the additives used for stabilization, are product specific. The special aggregate structure and high purity of the dispersed particles (AEROSIL fumed silica and AEROXIDE products) make our dispersions superior to other conventional colloidal systems.

If, as described in Section 2, an SiCl4 / AlC3 mixture (about 99:1) is hydrolyzed in one oxyhydrogen flame, mixed oxides are developed: AEROSIL MOX 80 and AEROSIL MOX 170, which differ from each other only in terms of the surface area. In this process, the aluminium oxide is incorporated as doping oxide directly into the primary particle of the host oxide (SiO2).



3.6

Surface Chemistry

H O Si
Figure 38:

In addition to the particle fineness of AEROSIL fumed silica, the large specific surface represents the most important characteristic of AEROSIL fumed silica. The latter depends as already discussed on the average size of the primary particles. Since the surface area of the AEROSIL fumed silica types is large in relation to the mass, the surface chemistry plays a significant role and determines many applicational properties.

O Si Si

Silanol groups (left) and siloxane groups (right)

3.6.1

Two Functional Groups Determine the Chemistry

The individual groups assembled in Figure 39 will be discussed in greater detail below. Initially, however, the determination of the silanol groups will be described because as mentioned, these groups are of special importance.

Fundamentally two functional groups, namely the silanol groups and the siloxane groups, can be differentiated from each other in the case of AEROSIL fumed silica, as shown in Figure 38. A hydrophilic character must be attributed to the silanol groups, i. e. these groups are water attractive and are responsible for the fact that AEROSIL hydrophilic types is easily wetted by water. Moreover, the possibility of producing AEROSIL hydrophobic types must be attributed to the chemical reacting capacity of the silanol groups. In contrast, the siloxane groups are largely inert chemically (i. e. non-reactive), and in addition a hydrophobic, in other words water repellent, nature must be attributed to them. However, in the case of the non-aftertreated AEROSIL types, the hydrophilic character of the silanol groups prevails. On the basis of these two functional groups, quite complex reaction chemistry develops under certain conditions. This can also be seen to stem in part from the fact that we must distinguish between the following groups: - free silanol groups - bridged silanol groups - geminal silanol groups - vicinal silanol groups - siloxane groups under tension and those less under tension.

O Si
free

O Si H

O Si

vicinal and bridged

H O Si
geminal
Figure 39:

O Si

O Si
siloxane group

Si02 surface groups, concentration data are given for example in Table 18, as well as in Figures 40 and 45



3.6.2

Determination of the Silanol Groups

The method results in meaningful and reproducible values. On the basis of the IR combination oscillation band of water at 5200 cm-1 or the Si-OH-bands between 3800 and 2800 cm-1 it can be concluded that, under the drying conditions given above, free and physically bound water is completely removed, whereby the splitting off of the silanol groups is still imperceptible (see overview in Table 16).

Due to the reacting capacity of the silanol groups, these groups can be determined quantitatively by various methods. In the literature, mainly the following methods are described to determine the SiOH concentration: - annealing of dried AEROSIL (49-51) - chlorination of SiOH (51-55) - conversion of SiOH with phenyl lithium (53), with diazo- methane (53, 56), and with alkylmagnesium halides (57) - conversion of SiOH with B2H6 (58,59) - conversion of SiOH with LiALH4 (60,61) - infrared spectroscopy (51, 54, 61 - 64)

-O-D -C-H - SiOH (isolated) - SiOH(bridged) - SiOH (bridged) proton acceptor - SiOH (bridged) proton donor - SiOH (combination oscillation) H2O

2760 2900-3000 3750 3000-3800 3715 3510 4550 5200

3.6.2.1 The Lithium Aluminium Hydride Method

After extensive comparative studies, it was determined that the conversion of dried AEROSIL fumed silica (1 h, 100 C, 10-2 mbar) with LiAlH4 is one of the most exact and simplest methods of determining the SiOH concentration on the AEROSIL surface:

Table 16:

Some important IR adsorption bands (cm-1) of pyrogenic silicas; precipitated silicas because of their high water content show strong uncharacteristic oscillation bands in the bridged SiOH range

As shown by Figure 40, the silanol group density is to a first approximation independent of the specific surface. With old material (storage time after production longer than 1 week, i. e. normal product) about 2.5 SiOH/nm2 are measured, see Table 18, page 43.

4 SiOH + LiAIH4

diglymes

Si - O - Li + ( Si-0)3 AI + 4 H2

The other methods of determination mentioned above are less reliable and have attained no importance.

1.5

When the lithium aluminium hydride method (also known as the

Silanol group concentration mmol/g

SiOH density
1.0 2

split off is found by a pressure measurement, and in this way the silanol group density is ultimately determined. Since the hydride ion as an attacking agent is very small and consequently highly reactive, all silanol groups on the surface including the bridged groups are detected. This corresponds with the determination of the residual silanol group density of AEROSIL hydrophobic types, which according to IR spectroscopic findings contains practically no free silanol groups any longer (see the IR spectrum of AEROSIL R 812 in Figure 6, page 13).

0.5

SiOH concentration

100

200

300
2

0 400

Specific surface m /g

Figure 40:

Total silanol group concentration on the AEROSIL hydrophilic products according to the LiAIH4 method

Silanol group density nm-2

lithium alanate method) is employed, the amount of hydrogen



Only in the case of AEROSIL OX 50 are lower SiOH densities found (about 2.2 SiOH/nm2), which must be attributed to the production process. In comparison with the other AEROSIL
Transmittance %

100 80 60 40 20 0 4000 3000

100 80 60 40 20 0 4000 3000 2000

-1

fumed silica types, this is produced at higher flame temperatures. As expected, the absolute concentration of the silanol groups rises linearly with the specific surface. This contributes substantially to understanding the greater thickening effect of the AEROSIL fumed silica grades with a high surface area (assuming a good dispersion), see Figure 68, page 57.

Wave number cm

Figure 41:

3.6.2.2 IR Spectroscopy
In addition to the LiAIH4 method, IR spectroscopy has recently gained importance for the qualitative as well for the quantitative determination of the silanol groups in the laboratory. IR spectroscopy, however, is not a suitable method for production control. Pressed tablets of pure AEROSIL fumed silica are used for the testing, (for example 13 mm diameter, 16 mg/cm2) which in the case of the hydrophobic material are pressed into a wire net to increase the stability. In Table 16, some important adsorption bands are listed. With the aid of the LAMBERT-BEER law,

IR spectroscopy tracking of the H-D exchange on AEROSIL 200 (left: starting material, right: after exchange)

The silanol groups react with D2O with an H-D exchange. IR spectroscopy makes it possible to monitor the reaction process (see Figure 41), and after analysis of the H2O/HDO/D2O mixture therefore permits a quantitative determination of the silanol groups (61). The results correlate well with the lithium aluminium hydride method. Furthermore, Figure 41 shows that a slight portion of the silanol groups (about 10 - 20 % internal SiOH groups) is not accessible for a deuterium exchange.

In Jo/J = cd
quantitative measurements of the free silanol groups are possible. Here, the quotient Jo/J is identical to the transmittance of the sample (at the relevant wave length), and the product cd refers to the density of the silanol groups (mol/cm2). The molar adsorption coefficient for free silanol groups (3750 cm-1) was determined by J. MATHIAS and G. A. WANNEMACHER (61) as (4.4 0.4) x 105 cm2/mol.



3.6.2.3 Morpholine Adsorption

One method of determination that detects only sterically accessible silanol groups is based on the adsorption of donor molecules such as, for example, morpholine (see also 3.6.3.3.). The course of the adsorption isotherms of morpholine of AEROSIL 200was studied by M. ETTLINGER, H. FERCH and J. MATHIAS (65). According to Figure 42, at a constant morpholine concentration the adsorption (mmol/g) is a function of the BET surface area. In contrast, analogous to the silanol group density, the morpholine coating density shows only a slight dependence on the specific surface (see Figures 40 and 42 on this point). However, with the morpholine adsorption method, lower coating densities are found. These discrepancies must be attributed to the different adsorption behavior of bridged and free silanol groups as well as to their steric accessibility.

The morpholine adsorption values of the AEROSIL hydrophobic types are shown in Table 17. AEROSIL types with chemically comparable groups have comparable adsorption values. AEROSIL R 202 and AEROSIL R 805 differ distinctly here. Due to the chain structure, by no means all silanol groups (LiAlH4) are sterically accessible. The greatest differences between the two methods of determination are displayed by AEROSIL R 805 (1.66 and 0.47 SiOH/nm2). In polar systems (for example 1.2-ethylene glycol, epoxy systems) AEROSIL R 202 and AEROSIL R 805 have comparably good thickening effect which is superior to that of the other AEROSIL fumed silica types (see Edition 27 in this series of Technical Bulletin AEROSIL on this point). In this connection, the chain structure evidently plays a dominant role.

3.6.3
1.2 1.0 0.8 0.6 0.4 0.2 0

Interparticular Interaction

1.2 1.0

In conjunction with the description of the rheological characteristics of dispersions containing AEROSIL fumed silica
Morpholine molucules nm2

Ads. morpholine mmol/g

or of the structure of pulverulent AEROSIL, the interactions between the SiO2 particles themselves and with the dispersion phase play a decisive role. In Edition 23 in this series of Technical Bulletin Pigments, the following possible interactions are discussed in greater detail: - VAN DER WAALS attractive forces (permanent or induced dipoles) - electrostatic interactions (COULOMB interactions) - gravitational interactions (negligible) - acid/base interactions as well as orbital interactions (important).

0.8 0.6 0.4 0.2 0

100

200

300
2

400

BET surface m /g

Figure 42:

Dependence of the morpholine adsorption on the BET surface of hydrophilic AEROSIL fumed silica types Cmorph = 0.1 mol/l , butanol/water 1 : 1) Surface group Dimethylsilyl Dimethylsilyl Trimethylsilyl Dimethylsiloxane Octyl Morpholine molecules per nm2 0.32 0.35 0.33 0.15 0.47 SiOH per nm2 LiAIH4 0.60 0.39 0.44 0.29 1.66

AEROSIL types R 972 R 974 R 812 R 202 R 805 Table 17:

Comparison of the silanol group density determined according to the morpholine adsorption and the LiAIH4 methods on hydrophobic AEROSIL types



3.6.3.1 Hydrogen Bridge Linkage

Hydrogen bond interactions are regarded as a subgroup of the acid/base interaction. According to a new model by E. R. LIPPINCOTT and R. SCHRDER (66, 67), the hydrogen bridge linkage is described by a superimposition of protomeric limiting structures. According to Figure 43, the proton has two stable options within the bond (68). The proton delocalization over the range of the two potential wells takes place by means of a tunnel effect at high frequency (comparable with the ammonia inversion oscillation).
Energy
Si O H H O H H Si O H O H

Similar reactions constantly take place on the AEROSIL fumed silica surface as well. The temporary structure of the AEROSIL agglomerates can be explained by the simple formation and breaking of hydrogen bridge linkages. Due to the (slight) silanol group density of about 2.5/nm2, no possibility exists for the formation of intramolecular bridges (in contrast to precipitated silicas). The presence of isolated silanol groups is supported by IR spectroscopic studies (70), so only intermolecular hydrogen bridges must be taken into consideration. Figure 44 shows a hydrogen bridge interaction between two AEROSIL primary particles in an enlargement true to scale.

Oxygen Hydrogen

Si

Distance between an O atom and the H atom

Si

Si Si

Figure 43:

Double potential minimum of the hydrogen bridge linkage between the O atom of a silanol group and the H atom of a water molecule (schematically, the O-O distance is held constant)

The energy of the hydrogen bridge linkage (4 - 40 kJ/ mole) depends on the OHO angle. It reaches a maximum when the three atoms are arranged linearly. In comparison with a covalent C-H bond (about 360 kJ/mole), the hydrogen bridge linkage is a moderately weak interaction. However, it is stronger than the VAN DER WAALS forces. In nature, hydrogen bonds play a quite decisive role. The mean kinetic translational energy in the case of the human body temperature is about 4 kJ/mole (69). The splitting and regeneration of hydrogen bonds are therefore elementary processes in the metabolism. Only due to the directional character of the H bonds can complicated molecular structures be maintained. At the same time, they permit a rapid structural change. Figure 44:

Si
Hydrogen bridge linkage between two idealized AEROSIL 200 primary particles in an enlargement true to scale

In the infrared spectrum, the frequency of the oscillations between the oxygen atom and the hydrogen atom in the OH bond decreases in the cases of bridged systems, which corresponds to a loosening of the OH bond (see Table 16 and Figures 6 and 41). The probability of finding a suitable neighbor for a silanol group for the purpose of forming an H bridge rises as the particle fineness increases. Therefore, the density of the free silanol groups (SiOH/nm2) decreases as the specific surface increases (Figure 45). This is also reflected in the dispersibility of AEROSIL fumed silica which decreases as the specific surface increases (also see Figure 68 on this point).

0

3.6.3.2

Moisture Balance

7 6

3.6.3.2.1 Moisture Balance at Room Temperature

Moisture adsorption %

Bag without PE lining

5 4 3 2 1
82 % rel. humidity 55 % rel. humidity

Water molecules can be fixed to silanol groups and thus to the AEROSIL fumed silica surface via hydrogen bridges, as discussed in the preceding section. Water vapor therefore has a relatively high affinity for AEROSIL hydrophilic types and is adsorbed well (wetting heat of water on AEROSIL 200: - 150 x 10 -7 J/m2; in comparison on quartz, which has a higher affinity for water in liquid form: - 610 x 10 -7 J/m2). The water adsorption from the atmosphere depends on the humidity of the air and is reversible (Figure 46). After storage conditions change, the atmospheric moisture is initially adsorbed remarkably quickly or given off again just as quickly. In practice, the establishment of equilibrium takes place slowly because in a bag of AEROSIL fumed silica the outer layers largely shield proportions lying more deeply inside. The moisture balance is then determined essentially by diffusion processes. This behavior can be demonstrated in a simple weathering experiment. For this purpose, test tubes filled with AEROSIL 150

Bag with PE lining (normal packaging)

10

20

30

40

50

60

70

10

20

30

Duration of weathering, days

Figure 46:

Moisture adsorption (storage at 82 % rel. humidity) and release (storage at 55 % rel. humidity) of AEROSIL 200 (10-kg bag, sealed, red curve: PE lining = normal packaging; blue curve: bag without PE layer)

are stored at an atmospheric humidity of 90 %. Due to the adsorption of water, the absolute values of the extinction measurements of the free and bridged silanol groups change. The change in the quotient of extinction bridged and free describes the progressive water adsorption. Figure 47 shows that the upper AEROSIL layer differs distinctly from the lower layer. The result can be explained only on the basis of a slow diffusion of moisture into the inner layers of an AEROSIL charge.
0.8

Free silanol group density nm-2

0.75

1.5

Extinction of the bridged silanol groups cm-1

Conc. of the free silanol groups mmol/g

SiOH density

160

0.7 0.6

Upper Layer

120

SiOH groups rel. bridged / free

0.5 0.4 0.3 0.2 0.1 0 0 20 40 60 80 100 120 140

0.50

1.,0

SiOH concentration
80

Lower Layer

0.25

0.5

Extinction
40

100

200

300
2

400

Specific surface m /g

Contact time h

Figure 45:

Silanol groups as a function of the specific surface of AEROSIL fumed silica (IR, samples 1 year old, method of determination (61))

Figure 47:

Comparison of the silanol group relationships in the lowest and uppermost layers of AEROSIL fumed silica in a test tube as a function of the duration of moistening (90 % rel. moisture)



The maximum water adsorption of AEROSIL hydrophilic types (thin layer) grows with an increasing specific surface, and therefore correlates with the concentration of the silanol groups. AEROSIL 380, with the largest BET surface area, naturally adsorbs the most water. In the case of the AEROSIL hydrophobic types, the silanol group concentration, and thus the moisture adsorption, are distinctly reduced (compare Figure 8). AEROSIL fumed silica is not hygroscopic. Although it adsorbs atmospheric moisture, it readily releases this moisture again under normal, slightly changed conditions. During each of these processes with an adequately long storage time equilibrium conditions are attained. At least 95 % of the water adsorbed after the genesis is removed by the simple application of vacuum (10-1 mbar), even at room temperature, which can be easily proven on the basis of the IR spectra. Solid, hygroscopic materials are known to have a tendency to deliquesce and form lumps, while AEROSIL fumed silica remains unchanged under the normal conditions mentioned.

Figure 48, the physically bonded water also becomes attached to the free silanol groups during storage, causing these groups to be converted to the bridged form.

3.6.3.2.3 Moisture Balance at Higher Temperatures

If AEROSIL 200 is heated, the concentration of free silanol groups rises up to a temperature of about 600 C (1.8 SiOH/nm2); simultaneously, the intensity of the bridged form decreases to zero (about 700 C), see Figure 49. Slight changes in the band form at 3750 cm-1 during the heating between 450 C and 1100 C are attributed by E. KNZINGER, P. HOFFMAN, and R. ECHTERHOFF (71) to a change in concentration of the geminal silanol groups (= Si(OH)2).
100 80 100 80 60 40 20 0 3000 4000 3000 Wave number cm-1

Transmittance %

60 40 20 0

3.6.3.2.2 Aging
The bond angle SiOSi in a siloxane bridge can vary within wide limits (120 - 180 (23), also see Section 3.1).

4000

Figure 48: Stressed siloxane bonds, for example, have increased reactivity in the presence of water:
2,0

IR spectra of AEROSIL 200; fresh sample (left), stored for 1 year (right)
80
Density

Si-O-Si

+H-O-H

SiOH
Density of the free silanol groups nm-2

As shown by Table 18, the silanol group concentration is increased due to this hydrolysis during the course of the storage time. The amount of water required for this is very slight (about 0.25 %). Immediately after the flame hydrolysis, AEROSIL fumed silica contains these amounts of moisture in the form of physically bonded water. As shown from the IR spectra in Isolated SiOH/nm Total SiOH/nm2 Table 18:
2

1,5

60

1,0

Extinction at 4500 cm-1

40

0,5
Extinction of the bridged silanol groups

20

3 days old 1.5 1.8

Stored 1 year 1.15 2.65

Method of determination IR LiALH4

200

400

600

800

1000

1200

Temperature C

Figure 49:

Silanol group density of freshly produced AEROSIL 200 and of AEROSIL 200 stored for one year (original bag)

Splitting off of silanol groups from AEROSIL fumed silica due to thermal treatment (IR monitoring, 1 hrs annealing time)



Integral extinction cm-1

The affinity of annealed AEROSIL fumed silica for water was tracked by spectroscopy in 1988 (71); the samples treated at 500 C to 900 C adsorb water more readily than the AEROSIL fumed silica annealed at 1100 C. Apparently, at high temperatures, stressed siloxane bridges can be converted by means of minor structural rearrangements to less stressed systems which are no longer accessible for a later hydrolysis. On the AEROSIL sample annealed at 1100 C, the simultaneous growth of two IR bands can be observed at 3715 cm-1 (proton acceptor) and 3510 cm-1 (proton donor). These intensities originate from a chemisorption of water, and must be assigned to Hbridged, vicinal OH groups. Longer bridging chains (OH)3, (OH)4, etc. are not observed. At lower tempering temperatures (about 900 C), the pure adsorption of water molecules at silanol groups present likewise becomes noticeable. AEROSIL fumed silica which was treated only at 450 C (or at even lower temperatures) shows an additional band at 3675 cm-1 during the reaction with water. Annealed samples do not show these oscillations, leading to the conclusion that such processes are irreversible at high temperatures. The reduced thickening effect of AEROSIL fumed silica treated at high temperatures must likewise be attributed to an irreversible loss of silanol groups, Figure 50.
3000

N H O Si
Hydrogen bridge linkage

N H O Si
Brnsted interaction (formation of salt)

Si
Lewisinteractions (complexing)

Figure 51:

Possible interfacial forms of the interactions between an amine and the AEROSIL surface

3.6.3.3 Other Adsorption Effects

It is known that amines enter into strong interactions with silicas (72). The adsorption of morpholine for the determination of the accessible silanol group density has already been discussed in Section 3.6.2.3. The possible interactions of an amine with the AEROSIL fumed silica surface are shown by Figure 51. A LEWIS interaction can take place only when a coordinative defect point is present on the surface (73). Through adsorption it is possible to bind active substances such as cardiac glycosides to AEROSIL 200; nevertheless, the avail-

2000

Viscosity mPa s

ability of the active substance is comparable with an AEROSIL fumed silica free powder (74). Thanks to many works by H. RUPPRECHT and colleagues, deliberate statements can be made about the adsorption of active substances on the AEROSIL fumed silica surface (75-84).

1000

100

200

300

400

500

600

700

800

900

1000

1100

Annealing temperature (5 h each case) C

Cationic tensides are preferably bonded by means of an ion exchange; the adsorption is pH-dependent (details, examples, and models are described in 65).

Figure 50:

Thickening effect of annealed AEROSIL 200 (UP resin, annealing times 5 hrs in each case)



The irreversible adsorption of polyethylene glycol (molecular weight 5,000,000) on AEROSIL hydrophilic types takes place primarily via hydrogen bonds between isolated silanol groups and the ether oxygen atoms of the polyethylene glycol (85). The adsorption on AEROSIL R 972 is comparable with that on the hydrophilic silica. Consequently, hydrophobic interactions with an uncharged polymer must not be neglected. Figure 52 shows the adsorption of a polyelectrolyte on AEROSIL 200 which results in the almost quantitative flocculation of the SiO2. In a 0.01 % AEROSIL 200 dispersion there is a true SiO2 solution. Only in a high acidic milieu is the solubility product exceeded, and sedimentation occurs.
0.1% dispersions
100 80

referring to the acidic strength of pure SiO2 vary very widely (86, 87). If we calculate pKs = 9.46 (87), and with the assumption that in one litre of SiO2 dispersion 150 mg are dissolved as Si(OH)4 a pH value of 6.1 is found. Moreover, it must also be considered with AEROSIL fumed silica that due to the production process (see under 2) slight amounts of hydrochloric acid strongly influence measurement of the pH value. Figure 54 shows that the determination of the pH value is disrupted by the presence of agglomerates in the case of a AERODISP fumed silica dispersion. In some cases, the measurement is made only after the centrifuging, i. e. on the AEROSIL fumed silica solution, and higher (or at least as high) pH values are found, such as those which would be assigned to a correspondingly pure HCl solution.

0.01% dispersions

Sediment volume cm3

60 40 20

250 200 150

Cl ppm

H2 O

HCI 32%

H2 O

HCI 32%

100 50 0 3.0

Figure 52:

Sedimentation experiments with a 0.1 % and a 0.01 % AEROSIL 200 dispersion (flocculant Nalco 8100-A; in each case after 1 hrs and 24 hrs standing time)

3.5

4.0

4.5

5.,0

5.5

pH value

6.0

6.5

7.0

7.5

8.0

3.6.3.4 AEROSIL fumed silica as an Acid

AEROSIL fumed silica is a very weak acid, i. e. the equilibrium in Figure 53 is shifted distinctly to the left. Data in the literature
H O

Figure 54:

H O

O O Si O O HO Si O Si O Si O Si O H O Si O Si O Si O Si O Si O Si O Si O HO H O O Si O O Si O Si O O H H

Si

Si

H O H Water H

H O

pH values measured on 4% aqueous AERODISP dispersions as a function of the total chlorid content (determined after dissolution in alkali) blue squares: 4 % aqueous dispersion (specification (41)); green stars: dispersion above after centrifuging; red dots: measurement on pure HCl solution; theoretical curve (pH = - log [Cl - 1])

O O Si O O O Si O Si O Si O Si O O Si O Si O Si O Si O Si O Si O Si O O O Si O O O O H

Si

Si

O H

This phenomenon is known as the suspension effect, and in the weakly acidic range (pH = 4.5 - 7) can result in considerable differences between the dispersion and the solution

Si O

Si

(about 2 pH units). According to (88), these discrepancies are attributed to the negativelycharged SiO2 particles and to the associated increase in the transport number of the positive counterions in the dispersion.

O H

Figure 53:

AEROSIL fumed silica as acid (schematic representation)



Since the silanol groups can split off protons, negatively charged boundary surfaces result. However, since the entire system of the dispersion is electrically neutral, compensation is made at the surface charge centres by counterions. While the first charge layer is fixed, the electrical potential around the particle in the area of a diffuse counterlayer slowly dies out. This drop in voltage is known as the zeta potential, see Figure 55.

Electronegative particle Nernst potential Zeta potential Elec. potential around the particle shearing surface Liquid shell Rigid shell around the particle Range of the diffuse counterlayer Fraction of positive ions Fraction of negative ions
Figure 55: Electrical double layer around an electronegative particle, definition of the zeta potential (89)



Figure 56 characterizes the course of the zeta potential of AEROSIL OX 50 in comparison with the Degussa special oxides as a function of the pH value. In this respect, all AEROSIL hydrophilic types show a comparable behavior in the strongly basic range, the proton dissociation is largely complete (zeta potential no longer changes), while the H+ splitting off in the strongly acidic medium is suppressed. In principle, AEROSIL hydrophobic types show a similar course of curves even when the absolute amounts of the zeta potential are small (about 10 mV), corresponding to the low SiOH group concentration. The positive charge especially of AEROXIDE Alu C and VP Zirconium Oxide can be recognized well in the graph.
80 60 40 20

3.6.4

The Aftertreatment a Chemical Anchoring The Chemical Aftertreatment Some Bibliographic Examples

3.6.4.1

In the literature, numerous chemical reactions with AEROSIL fumed silica have been described. As examples, some of these reactions will be reviewed in the following sections.

3.6.4.1.1 Amination
Ammonia can be induced to react with AEROSIL fumed silica. In die temperature range up to 500 C the formation of singular (Si-NH2) groups and geminal Si(NH2)2 groups can be observed as the result of the substitution of OH groups or the dissociative opening of reactive siloxane bridges (90):

VP Zirconium Oxide AEROXIDE Alu C AEROXIDE TiO2 P 25

Zeta potential mV

0 -20 -40 -60 -80 2

AEROSIL OX 50

SiOH + NH3 Si - O - Si + NH3

5 6 7 8 9 10

Si - NH2 + H2O Si - NH2 + SiOH

pH value

For technical purposes, this and similar reactions have no significance.

Figure 56:

Zeta potentials of pyrogenic oxides produced by Degussa AG as a function of pH value (0.02 m KNO3 )



3.6.4.1.2 Reactions with Alkoxysilanes

The chemical reaction of pyrogenic silica with methoxysilanes is catalyzed by amines. Basic amines with exchangeable hydrogen atoms have the highest effectiveness (91). Here, two possible transition states must be discussed, and are presented in Figure 57. Slight amounts of H2O can likewise support the methanolysis (92). The primary product of the reaction of AEROSIL fumed silica with dimethyldiethoxysilane at room temperature is an H-bridged adduct, whereby the O atom of the silane functions as donor (92). Of the final products possible in principle: Si-OSi(CH3)2(OH) and (Si-0)2Si(CH3)2 (at 400 C), the former is more readily formed. Figure 57:

Me

H H

Me Si

O O

H N H Me

- NH3 Me H N O Me H Si O H H - CH3OH

Si O

3.6.4.2

AEROSIL Hydrophobic Types

Possible transition states during the amine-catalyzed reaction of trimethoxymethylsilane with the SiO2 surface; A: penta-coordinated transition stage B: 6-centre transition state

Expressed in greatly simplified terms, AEROSIL hydrophobic types is understood to mean a material which is not wetted by water; in other words it floats on the surface of the water.

CH3 H O Si H 2 Cl Cl
DDCS H2O + 4 HCI

CH3

CH3 Si CH3

Si H3C Si O CH3 O O Si Si

3.6.4.2.1 Conversion from Hydrophilic to Hydrophobic

The first industrially-produced hydrophobic silica was introduced onto the market in 1962, and has been designated AEROSIL R972 since KLOSTERKTTER reported in 1965 (93) that this

O Si

Hydrophilic AEROSIL
Figure 58:

Hydrophobic AEROSIL

Schematic representation of the reaction of dimethyldichlorsilane with the silica surface: conversion from hydrophilic to hydrophobic

material causes no silicosis in animal experments. Freshly-produced hydrophilic AEROSIL 130 is converted with dimethyldichlorosilane in a fluid-bed reactor according to Figure 58. The silane reacts with the silanol groups primarily with the formation of Si-O-Si (CH3)2 units (94), and as a result the material acquires a hydrophobic character. The number of silanol groups is reduced during the treatment of about 30 %

of the initial value. Analogous reactions can also be carried out with other silanes as shown by Figure 58. For example, when dimethyldichlorosilane is replaced by hexamethyldisiloxane as coreactant. The commercial product which is developed is known as AEROSIL R 812. An overview of all hydrophobic commercial AEROSIL products with their surface groups is given in Figure 7.



No serious difference between AEROSIL hydrophilic and hydrophobic types can be recognized from TEMs and SEMs, as shown
Tensile strength N/mm2

10 8 6 4 2

by Figure 22. In contrast, the water vapor adsorption isotherms differ dinstinctly. Figure 8 shows, for example, that AEROSIL R 202, in comparison with its base silica AEROSIL 150, adsorbs distinctly less water. Further possibilities for differentiation and characterization are discussed in detail in Technical Bulletin Pigments, Edition 18, entitled The Use of Hydrophobic AEROSIL in the Coatings Industry. As a result of the reduced silanol group density, the AEROSIL hydrophobic types show, among other things, a different dispersion and thickening behavior in comparison with hydrophilic types. The measurement values in Table 19 show, for example, that AEROSIL hydrophobic types can be dispersed more easily than AEROSIL hydrophilic types, even though the thickening effect is less pronounced. This last fact makes a high proportion of filler possible for the first time in many cases; a high proportion of filler is necessary for reinforcing characteristics, for example in cable gels for light conductivity fibres. This situation is additionally represented in Figure 59 where a silicone rubber is used as an example. AEROSIL 130 AEROSIL R 972 AEROSIL 200 AEROSIL R 974 Table 19: 3 % AEROSIL Viscosity in mPa s 3 Vu = 6,3 9,000 1,000 2,200 2,600
After minutes

SIPERNAT 160 AEROSIL 200

AEROSIL 300 AEROSIL R 974 AEROSIL R 812

Figure 59:

Mechanical characteristics of silicone vulcanizates with various silicas as filler (SIPERNAT 160 = a precipitated silica); formulation: 100 parts Silopren VS (GE Bayer Silicones GmbH & Co. KG), 40 parts silica, 0.5 % bis-(2.4 - dichloro benzoyl) peroxide

at m/s

10 Vu = 15,3 19,000 1,100 28,000 3,300

Comparison of the thickening effect of AEROSIL hydrophilic and hydrophobic types resulting from different dispersing intensity (mineral oil PKW F 4/7; Concentration of AEROSIL: 3 %; Vu: circumferential speed)



3.6.4.2.2 The Chemical Anchoring

The reaction of a silane with a silica surface is often not clearcut, but instead can result in different surface groups. The surface structures conceivable in principle have already been presented in Figure 7. The exact study of this chemistry was made possible, among other factors, by the progress achieved in 29Si-CP-MAS-NMR spectroscopy. Figure 60: In Table 11, some Si-NMR
29 29

50

-50 ppm

-100

-150

Si-CP-MAS solid matter NMR spectrum of AEROSIL R 974 groups can likewise be tracked by means of solid matter NMR spectroscopy (13C,29Si) because alcohol that has been split off appears only as a diffuse peak. In the case of AEROSIL R 202, the
29

chemical shifts are given which permit an association with the M, D, and T groups. If the 29Si-NMR spectrum of AEROSIL R 974 in Figure 60 is evaluated with this information, it is found that the D4 group is formed with greater frequency compared with D1 , D2 and D3 (see Table 10). The surface group sketched in Figure 58 therefore represents the most readily formed structure of AEROSIL R 972 and AEROSIL R 974 under the reaction conditions selected. If alkoxysilanes are used during the hydrophobic conversion, for example, in the case of AEROSIL R 805, the fixing of the silane at the SiO2 skeleton and the methanolysis of the alkoxy

Si-NMR spectra show the chemical fixing of the polydimethyl-

siloxane units. The peak splitting must be attributed to the presence of cyclic and chain-like structures, and even statements on the mobility of the chains are possible on the basis of the relaxation times. In conclusion, it should be emphasized that in the case of AEROSIL hydrophobic types no fractions of free silanes have been detected to date (IR, NMR, Headspace analysis, 100 C).



3.6.4.2.3

Dry Water and Aqueous Dispersions with AEROSIL Hydrophobic Types

AEROSIL hydrophobic types normally floats on water, it is not wetted by water, it is therefore water repellent. However, if water is divided into fine droplets in the presence of AEROSIL hydrophobic types, the hydrophobic silica envelopes the water droplets and prevents them from uniting. In this way a powdery substance is formed, the so-called dry water which Figure 61 shows in the form of an optical micrograph. If the water droplets are reduced in size still further, they are capable of by-passing the hydrophobic methyl groups, and reaching the silica base and thus the hydrophilic anchor points (residual silanol group density). Partial wetting results, and air is entrapped simultaneously. Such aqueous dispersions with AEROSIL hydrophobic types can be produced in the case of AEROSIL R 972, AEROSIL R 974, and AEROSIL R 805 up to a 20 % SiO2 content. Figure 62 shows, among other things, a 2 % AEROSIL R 812 dispersion. Figure 61: Optical micrograph of dry water based on 3 % AEROSIL R 812

Figure 62:

AEROSIL dispersions. Left: 2 % AEROSIL 200 in water; centre: 2 % AEROSIL R 812 in water; right: aqueous dispersion with 2 % AEROSIL R 812 (the amount of water is always the same)

0

4.

Statistical Quality Control

Conformity with the specification limits placed on AEROSIL fumed silica is ensured through a comprehensive quality control system. A multitude of individual measurements is compiled not only during production, but also during the actual quality control of the finished product in our own main laboratory.

340

OSG
320 300 280

X
USG

260

20

40

60

80

In order to be able to understand the flood of data, a statistical analysis is imperative. Figure 63 shows such an analysis as an example. It provides an impression of the progress of the individual measurements with respect to time, and describes the distribution of the measurement values. An important parameter here is the capability index, Cpk, which describes the width of the distribution with regard to the specification limits. If the process is under control, the Cpk value 1.
USG

5 17 11 7 1 2 12 13 7 3

X
OSG

n s

X min X max

80 304.47 5.03 291.0 318.0 270.0 330.0 0.00 % 0.00 % 0.00 % 1.990 1.694 0.335 2.495 1.163

USG OSG
n < USG n > OSG n

0 0 0

< < <

Cp
Cpk

Slope
Convexity

270
Figure 63:

279

288

297

306 315 324

Geary`s no.

Statistical quality control using AEROSIL 300, BET surface, as an example n = number of measurement values, x = mean value, s = standard deviation, USG= lower specification limit, OSG = upper specification limit, Cpk = capability index



5.

AEROSIL Types

6.
6.1

Applicational Effects
Reinforcement

The characteristic properties and main fields of use of the AEROSIL individual types are compiled in Table 20.

In all elastomers AEROSIL fumed silica develops a considerThe hydrophilic AEROSIL 200 or the hydrophobic AEROSIL R 972 can be recommended for fundamental experiments. These products represent the standard AEROSIL types. As already mentioned frequently in the preceding sections, the dispersion plays an important role in the use of AEROSIL fumed silica. The dispersibility decreases in the following order: AEROSIL OX 50 AEROSIL 90 AEROSIL 130 AEROSIL 150 AEROSIL 200 AEROSIL 300 AEROSIL 380. In general, hydrophobic AEROSIL fumed silica is much more easily dispersed. The advantage of AEROSIL high-surface types such as, for example, the high particle fineness, high transparency, strong reinforcing effect, and strong thixotropizing effect can be utilized only when the necessary dispersing power is developed (dissolvers, rotor-stator aggregates, pearl mills, triple roller mills, etc.). In moisture-sensitive systems, AEROSIL hydrophobic types also offers in addition to the easy dispersibility the advantages of a water-repellent effect. Before the actual dispersing, the AEROSIL fumed silica must be wetted by the dispersing medium, it must be incorporated. The incorporation time can be shortened when the compacted product is used (supplement V in the designation). Almost all AEROSIL fumed silica types (see physico-chemical data on AEROSIL, Page 78) are available in a compacted variant of, for example, about 120 g/l. It must be taken into consideration, however, that the dispersibility is somewhat reduced by the compacting process. The fundamentals of the reinforcing must be attributed to interactions with silanol groups and to the radical splitting of Si-methyl bonds followed by incorporation of the fragments into the polymer (95). Quite low concentrations of AEROSIL fumed silica are adequate for adjusting the rheological properties and can be used in coating systems to achieve a significant mechanical reinforcement of the paint film. AEROSIL fumed silica brings about an increase in the glass transition temperature of the coatings. This reinforcement effect also makes itself apparent in higher shear and E-moduli. The effect is thought to be caused by a considerably restricted mobility of the polymer chain segments, which results from a strongly adsorptive bonding of the binder molecules at the surface of AEROSIL fumed silica (103). able improvement in the mechanical characteristics such as the tensile strength, tear propagation strength, or tear initiation strength. Typical fields of use are HTV and RTV silicone rubber, fluoroelastomers, and NR (natural rubber) and SBR (styrenebutadiene rubber). In this series of Technical Bulletin Pigments, Editions 12 and 63 discuss these applications in detail.



Standard types

Special types AEROSIL OX 50

Type with a low specific surface and only slight tendency to agglomerate.

Hydrophobic types AEROSIL R 202

Thickening and thixotropizing of epoxy resins and special UP and PU systems.

AEROSIL 90
Silica with a low surface area for the reinforcing and thixotropizing of RTV silicone rubber. Especially well-suited to attaining high degrees of filling and/or to increase extrudability.

AEROSIL TT 600
Pronounced agglomerates, is especially well suited for the flatting of special systems.

AEROSIL R 805
Thickening and thixotropizing of epoxy resins. Used especially in adhesive and multilayer systems.

AEROSIL 130
Silica for the thickening, thixotropizing, and reinforcement of cold-curing sealants.

AEROSIL MOX 80
Mixed oxide of silicon dioxide with about 1 % aluminium oxide. Slight thickening effect in aqueous systems. Serves, among other purposes, for the production of dispersions.

AEROSIL R 812, AEROSIL R 812 S

Very finely divided, hydrophobic fumed silica. Regulation of the sagging behaviour of conventional and highsolids coatings. Highly effective free-flow aid. Thickening and thixotropizing of vinyl ester resins. Reinforcing silica for High strength and LSR systems.

AEROSIL 150
Same application as AEROSIL 130, but with higher reinforcing effect and improved transparency.

AEROSIL 200
Most frequently used type of AEROSIL fumed silica for thickening, thixotropizing, and reinforcement. A widespread application is also the adjustment of the flowability of pulverulent substances.

AEROSIL MOX 170

Likewise a mixed oxide with about 1 % aluminium oxide, but with smaller particles.

AEROSIL R 972
Hydrophobic fumed silica with a low specific surface. Well suited for the improvement and maintenance of the flowability of powders. Thickening of water-resistant systems. Use in anticorrosive paints. Improvement in the hydrophobicity and rheology of offset inks. Reinforcing silica for cold-curing silicone rubber.

AEROSIL COK 84
Mixture of AEROSIL fumed silica and highly dispersed aluminium oxide in the ratio of 5:1 for the effective thickening of aqueous systems and other polar liquids.

AEROSIL 300
The high specific surface causes a more pronounced thickening and thixotropic effect. An important field of use is in hot-vulcanizing silicone rubber.

AEROSIL 380
AEROSIL type with the highest specific surface. Used, for example, in transparent polyester resin coatings.

AEROSIL R 974
Use similar to AEROSIL R 972. Due to a larger surface, a higher thickening and thixotropizing effect as well as greater transparency are attained.

Table 20:

Characteristic properties and mainfields of use of the individual types of AEROSIL fumed silica



The most important and quantitatively the largest field of use for highly dispersed materials is represented by the reinforcement of rubber. A theory to explain the reinforcing effects is based on the so-called bound rubber effect, which has been known since 1929 (96). The expression, bound rubber is understood to mean that fraction of polymers which becomes insoluble in organic solvents when the previously soluble polymer is mixed and masticated with highly dispersed materials. Figure 64 shows a TEM of bound rubber structures which were derived in natural rubber with AEROSIL 200. The bound rubber fraction increases as the primary particle size decreases. This is in agreement with practice because it has long been known that more finely divided materials offer an improved reinforcing effect (97). Some mechanical characteristics of silicone vulcanizates with various silicas are shown by Figure 59. Even though the function of AEROSIL fumed silica as a reinforcing filler in silicone compounds is the most significant, AEROSIL fumed silica induces striking improvements in the mechanical characteristics in other systems as well, for example AEROSIL 200 in polyisobutylene. This plastic, which has only a slight permeability to gas, serves, for example, as material for spacers between glass window panes.
Static period Shearing Static period

Figure 64:

TEM of bound rubber of AEROSIL 200 in natural rubber. Mixing ratio 30 parts to 100 parts rubber. Swelling agent and solvent: benzene (30)

Viscosity

Time

Figure 65:

Thixotropy = decrease in the viscosity during the shearing time, and increase again during the static period (schematic)



6.2

Thickening

If AEROSIL fumed silica is dispersed in a liquid, the surface silanol groups interact with each other either directly or indirectly via the molecules in the liquid. This affinity must be attributed to the hydrogen bridge linkages (see 3.6.3.1), and results in a temporary, three-dimensional lattice structure becoming macroscopically visible as thickening. Under a mechanical stress, for example due to intensive stirring or shaking, the structure is broken down again. The system becomes more fluid, in other words the viscosity drops. In the static state AEROSIL fumed silica particles join again, and the viscosity regains its original value. This process is termed thixotropy, and is represented schematically in Figure 65.
Carbon tetrachloride Dibutyl phthalate

Primary particles (idealized)

Aggregates

rest shearing

Agglomerated aggregates

Three-dimensional network

Figure 66:

Schematic representation of the interaction between AEROSIL fumed silica particles in liquids
Methyl Benzene acetate

It is possible to imagine the build-up and breakdown of the three-dimensional network structure as shown schematically
Viscosity mPa s

104
8 6 4 2

Acetone water Butanol

in Figure 66. As evident from Figure 67, the thickening and thixotropizing effect of AEROSIL fumed silica depends on the polarity of the system, whereby the best results are attained for the most part in non-polar systems. In this connection, the term polarity should be understood to mean the ability of the molecules in the liquid to form hydrogen bonds (also see (98) on this point). AEROSIL COK 84 has proved to be very suitable for adjusting the rheology of highly polar substances such as water, dimethyl formamide, etc.

103
8 6 4 2

102

10

12

14

AEROSIL content %

Figure 67:

Thickening of various liquids with AEROSIL 200



The thickening and thixotropic effect of AEROSIL fumed silica at a given concentration depends to a great extent on the intensity of the dispersing. With vane or propeller stirrers, adequate degrees of thickening can perhaps be attained, but other factors such as the rheological long-term behavior are unsatisfactory in many cases. Good results are achieved with high-speed stirrers. The best results, however, can be attained with rotor-stator aggregates or with a triple roller mill. In principle, it can be established that the thickening effect increases with a rising BET surface. However, with an increasing fineness of the particles, a greater dispersion intensity is required in order to attain the possible thickening at all. This complex of problems is represented once again in Figure 68. Due to the specific interactions of silicas with polymers, a further reaction mechanism must be taken into accout in connection with the rheological effect of AEROSIL fumed silica in paints and other coating systems. The polymer molecules are adsorbed at the AEROSIL fumed silica surface in loop and coil conformations, and the mobility of the chain segments is restricted over and beyond the interface polymer/silica, as a result of the entangled polymer chains. This causes a reversible structure to be formed based on entropy elasticity. Figure 69: The rheological characteristics, such as thickening effect, structural viscosity and thixotropy of paints and coatings containing AEROSIL fumed silica can be well explained with the aid of this mechanism (103). Additional information relating to this subject may be found in Technical Bulletin Pigments No. 23 and 53.
Viscosity m Pa s

4000 3500 3000 2500 2000 1500 1000 100

150

200

250

BET surface m /g

300

350

400

Figure 68:

Dependence of the viscosity on the BET surface (2 % AEROSIL fumed silica in LUDOPAL P 6 (BASF AG), dissolver 5 min., 6.3 m/s, 5 % batch)

Comparison of the sedimentation tendency of zinc dust paints based on an epoxy ester after a storage time of four weeks at room temperature. Left: control paint; right: paint produced using 2 % AEROSIL R 972. Composition: JGALYD ED 4, 50 % in xylene 19.6; zinc dust superfine 72.5; butanol 1.0; SHELLSOL A 9.4; Co octoate, 6 % Co 0.2



6.3

Antisetting Agent

AEROSIL fumed silica as a Free-Flow Aid Particle fineness Coating (ball bearing effect) Spacers Adsorption of water Moisture protection No reaction No def. agglomerates High surface area Hydrophobicity Chemically inert Table 21:

In liquids containing solid matter, for example pigmented coatings, AEROSIL fumed silica prevents or delays a sedimentation. In general, addition of small amounts are adequate to attain the desired antisettling effect, which as a rule is accompanied by a certain increase in viscosity. It is obvious that the improvement in the suspension behavior must essentially be attributed to the thixotropic AEROSIL fumed silica lattice structure, because a pure increase in viscosity alone does not result in success, as can be recognized in Figure 69. In comparison with the use of AEROSIL 200, and all AEROSIL hydrophobic types offer the advantage that they are not so strongly agglomerated, and therefore they can be dispersed more easily. AEROSIL COK 84 is best suited for holding solid matter particles in suspension in water. For example, with about 3 % AEROSIL COK 84 it is possible to stabilize aqueous diamond suspensions that are used as polishing agents. In some cases, a sedimentation is intentionally accepted because the solid matter particles are coated by AEROSIL fumed silica, and consequently the sediment is loosened up and set to a consistency that is easily redispersible. Use is made of this effect, for example, in zinc dust paints (99), flowables, or lotions.

Active mechanisms when AEROSIL fumed silica is used as free-flow aid with powders

The active mechanism of AEROSIL fumed silica as a free-flow aid are compiled in Table 21. Details on the subject of Free Flow such as mixing techniques, measurement methods, and concrete examples of application are given in Edition 31 in this series of Technical Bulletin AEROSIL entitled AEROSIL for Improving the Flow Behaviour of Powder Substances. In conclusion here, Figure 70 should be pointed out; this figure shows an extremely simple, but nevertheless meaningful measurement method with viscosity vessels resembling hourglasses. When this method is employed, powders with good flow behaviour still flow out of the glass vessels with a small discharge opening.

6.4

Free Flow

The packaging, storage, and handling of substances in powder form are made difficult due to the agglomeration and caking of the solid matter particles. In industry, however, a good flow behaviour of the powders and good storage stability are required even at high atmospheric humidity and when the powder are subjected to compression stress. The following can be discussed as mechanism of adhesion between the powder particles: - VAN DER WAALS forces - electrostatic forces - liquid bridges - solid matter bridges - entanglement. Figure 70: Series of measuring vessels to evaluate the flowability without compression stress



6.5

Thermal Insulation

In the temperature range of 50 - 130 C in the case of AEROSIL 380, the loss due to radiant heat makes up to 10 % of the total heat loss, while the rest must be attributed to gas conduction. At higher temperatures (about 800 C) it is expected that the radiation contribution will rise sharply to over 50 % (102). AEROSIL fumed silica also serves for low-temperature insulation, and here also the same characteristics are of importance. Powder mixtures or moulded articles containing AEROSIL fumed silica are used, for example, to insulate storage heaters, aircraft turbines, pipelines on ships and in power plants, as well as tanks for liquid gases. The best effect is attained through the use of AEROSIL 300 and AEROSIL 380.

Amorphous silicon dioxide is a very poor conductor of heat. Especially in the insulation range up to 1000 C, AEROSIL fumed silica has proven very successful. The particle fineness of AEROSIL fumed silica makes charges possible with void volumes lying in the range of the mean free path length of the nitrogen and oxygen molecules (about 20 nm, 30 C), and consequently the gas conduction is reduced to a minimum. In principle, the following contributions must be considered in connection with the thermal conduction in highly dispersed powders (100): - thermal radiation - solid-solid conduction - gas conduction - natural convection

6.6

AEROSIL Fumed Silica as a Versatile Product for Solving Problems

In the compilation in Table 22, the different effects of AEROSIL Because of the small pore size the natural convection (101), and because of the small solid matter volume fraction the solid-solid conduction as well, can to a first approximation be neglected. Cause Interaction between AEROSIL fumed silica particles Effect Rheology: thickening, thixotropizing Rheology: antisetting agent Rheology: suspension stabilizing Rheology: emulsion stabilizing Reinforcing Particlefineness Flowability Storage stability Adsorption Thermal insulation Coating Polishing agent Grinding aid Dispersing aid Antiblocking Purity Hydrophobicity Raw material Transfer of the hydrophobic characteristics to other systems fumed silica are traced back to basic causal physico-chemical characteristics of the pyrogenic silica. Some applicational examples round off the picture. Examples Coatings, UP and EP resins pastes, resists, blood fractioning, maintenance-free batteries, etc. Zinc dust paints Drilling fluids, diamond suspension Oil + water Silicone rubber Table salt Fire extinguisher powder of glycoproteins Storage heaters of neon tubes, diazo papers Silicon disks Pyrotechnics Colour pigments Polyester films
Highly pure glasses, light-conduct. fibres

Hydrophobic conversion defoaming agents

Table 22:

AEROSIL fumed silica as a versatile partner



7.

Physiological Behaviour and Industrial Safety

of cream). The MAK value (maximum concentration at the work place) in the Federal Republic of Germany for pyrogenic silica currently lies at 4 mg/m3 (inhelable fraction) total dust during an evaluation time of 8 hours. In Edition 28 in this series of Technical Bulletin Fine Pigments all questions regarding the handling of synthetic silicas are discussed, including the technical possibilities which can ensure compliance with an established MAK value. Oral intake, human Intact human skin Inhalation, human Inhalation, rat LD50, rat Eye irritation, rabbit Skin irritation, rabbit Intact rabbit skin Table 23: no finding no finding no silicosis no silicosis 3300 mg/kg no effects no effects no effects

Due to its X-ray amorphous structure, AEROSIL fumed silica causes no silicosis. Among the employees in the production plants, who in part have come into contact with these substances for decades and who are subject to strict medical supervision, no signs of silicosis have been determined. In addition, humerous inhalation experiments on animals did not show any signs of silicosis. This series of Technical Bulletin Fine Pigments discusses the complex of questions mentioned above in detail in the edition entitled Silicosis Caused by Amorphous Silica? (Edition 76) and The Biological Effects of SiO2, Al2O3 and TiO2 (Edition 64). Table 23 summarizes some biological effects of AEROSIL 200 on animals. Administered orally, AEROSIL fumed silica passes through the gastrointestinal tract without being resorbed in detectable amounts. On the skin as well, AEROSIL fumed silica is harmless. It can occasionally cause a feeling of dryness, but this feeling can be easily eliminated by washing and normal skin care (application

Toxicological effects of AEROSIL 200 on animals



8.

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(53) H. P. BOEHM, M. SCHNEIDER, Z. anorg. allg. Chem. 301, 326 (1959) (54) J. UYTTERHOEVEN, H. NAVEAU, Bull. Soc. chim. France 27 (1962) (55) J. A. HOCKEY, Chem. and Ind. 9, 57 (1965) (56) G. BERGER, Chem. Weekbl. 38, 42 (1941) und K. H. HERBERT, Mh. Chem. 88, 275 (1975) (57) M. V. TONGELEN, Bull. Soc. chim. France (2318) (1965)

(80) H. RUPPRECHT, M. J. BIERSACK, G. KINDL, H. LIEBL, Pharm. Ind. 38, 1009 (1976) (81) H. RUPPRECHT, H. LIEBL, Pharm. 30, 101 (1975) (82) H. RUPPRECHT, H. LIEBL, Koll.-Z.Z. Polym. 239, 685 (1970) (83) H. RUPPRECHT, H. LIEBL, Arch. Pharm. 307, 817 (1974) (84) H. RUPPRECHT, Progr. Coll. Polym. Sci. 65, 29 (1978) (85) J. RUBIO, J. A. KITCHENER, J. Coll. Interf. Sci. 57,132 (1976)

(58) H. DEUEL, G. HUBER, Helv. chim. Acta 34, 169 (1951) (86) N. INGRI, Nobel Symp. 1977, 40, 3 (1978) (59) M. BAVEREZ, J. BASTICK, Bull. Soc. chim. France 3226 (1965) (60) H. J. WARTMANN, Dissertation ETH Zurich (1958) (61) J. MATHIAS, G. WANNEMACHER, J. Coll. Interf. Sci. 125, 61 (1988) (62) R. S. MCDONALD, J. Physic. Chem. 62, 1168 (1958) (89) H. J. JACOBASCH, H. KADEN, Z. Chem. 23 (3), 81 (1983) (63) G. WIRZING, Naturwiss. 51, 211 (1964) (64) M. BAVEREZ, J. BASTICK, C. R. Acad. Sci. Paris 260, 3939 (1965) (65) M. ETTLINGER, H. FERCH, J. MATHIAS, Arch. Pharm. 320, 1 (1987) (66) E. R. LIPPINCOTT, R. SCHRDER, J. Chem. Physics 23, 1131 (1955) (67) E. R. LIPPINCOTT, R. SCHRDER, J. Physic. Chem. 61, 921 (1957) (68) G. KORTM, Lehrbuch der Elektrochemie, Verlag Chemie (1972) (69) J. A. CAMPBELL, Allgemeine Chemie, Verlag Chemie (1975) (70) R. S. MCDONALD, J. Physic. Chem. 62, 1168 (1958) (71) E. KNZINGER, R. HOFFMANN, R. ECHTERHOFF, Mikrochim. Acta 2, 27 (1988) (72) M. J. CHILD, M. J. HEYWOOD, G. H. YONG, C. H. ROCHESTER, J. Chem. Soc. Farad. Trans. 1, 78, 2005 (1982) (73) W. POHLE, P. FINK, Z. Phys. Chem. (N. F.) 109, 77 (1978) (74) F. GSTIRNER, W. FREISEL, Pharmaz. 32, 965 (1970) (75) E. ULLMANN, K. THOMA, H. RUPPRECHT, Arch. Pharm. 301, 357 (1968) (76) H. RUPPRECHT, H. LIEBL, E. ULLMANN, Fed. Intern. Pharm. London, 7.-12. 9.1969 (101) R. P. TYE, Thermal Transmission Measurements of Insulation, ASTM STP-660 (1978) (102) H. S. CHU, A. J. STRETTON, C. L. TIEN, Int. J. Heat Mass Transfer 31, 1627 (1988) (103) U. CHRIST, A. BITTNER, farbe + lack, 98, 829 (1992) (97) G. KRAUS, Reinforcement of Elastomers, Wiley: New York (1965) (98) H. BRNNER, E. WAGNER, Angew. Chem. 72, 744 (1960) (99) Technical Bulletin Pigments No. 18, Company publication, Degussa AG, Frankfurt, 5th edition (1989) (100) H.-S. CHU, C.-J. TSENG, J. Thermal Insulation 12, 108 (1988) (90) P. FINK, I. PLOTZKI, G. RUDAKOFF, Wiss. Ztschr. FriedrichSchiller-Univ. Jena, Naturwiss. R., 37, 911 (1988) (91) J. P. BLITZ, R. S. S. MURTHY, D. E. LEYDEN, J. Coll. Interf. Sci. 126, 2 (1988) (92) W. POHLE, Z. phys. Chemie, Leipzig 269, 1228 (1988) (93) W. KLOSTERKTTER, Arch. Hyg. Bakt. 149, 577 (1965) (94) H. BRNNER, D. SCHUTTE, Chem.-Z. 89, 437 (1965) (95) G. KOERNER, M. SCHULZE, J. WEIS, Silicone, Chemie und Technologie, Symposium 1989, Vulkan-Verlag, Essen (96) J.H.FIELDING, Ind. Eng. Chem. 21, 1027 (1929) (87) P. CHRISTOPHLIEMK, R. FAHN, H. FERCH, A. KREHER, K.-H. WORMS, WINNACKER, KCHLER, Chemische Technologie Band 3, Anorganische Technologie II, 4. Auflage S. 57 (1983) (88) G. LEE, D. DICK, E.-M. VASQUEZ, K. WERNER, Drug Develop. Industr. Pharm. 15 (4), 649 (1989)



9.
AAS

Brief List of Technical Terms

Agglomerates
Loose clusters of primary particles and/or aggregates which can be broken apart during dispersing (DIN 53 206).

Abbreviation for Atomic absorption spectroscopy. Analysis process based on the fact that a light quant emitted by an excited atom can be absorbed by a non-excited atom of the same element.

Aggregates
According to DIN 53 206, intergrown union of particles bonded at the interfaces whose surface area is smaller than the sum of the total surface areas of the primary particles.

Adsorption
describes the retention of a material at the inner and/or outer surface of a solid (DIN 28 400).

Adsorption isotherms
show correlations between the amount of substance adsorbed at the adsorbate and the concentration or partial pressure of the gas to adsorbed in the state of equilibrium at a constant temperature.

Alveoli
Air cells of the lungs (location where exchange of gas takes place between inhaled air and the lung tissue).

Alveoli-penetrant
Particles which due to their size can penetrate into the alveoli.

AERODISP
Under the trademark AERODISP Degussa manufactures AEROSIL fumed silica and metallic oxide dispersions in water and organic solvents e.g. ethyleneglycole.

AMES-Test
Named after Bruce AMES, who in 1972 described a method used to study the mutagenic effect of materials on certain strains of bacteria.

AEROPERL
is a spherical granulate of AEROSIL or metallic oxides with a high density and a constant large surface area. The microgranulate has excellent flow properties and can be handled with low dust generation.

Amorphous
Unformed, without structure, in contrast to crystalline.

Arc silica
Pyrogenic silica produced by reduction of quartz sand with coke in an electric arc furnace and subsequent oxidation of the SiO formed.

AEROSIL
Registered trade name owned by Degussa AG for synthetic, highly dispersed silicas which are produced by the high-temperature hydrolysis process.

Cardiac glycoside
Compounds of types of sugar with non-sugar components which can increase efficiency of the heart.

AEROXIDE
Registered trade name owned by Degussa AG for synthetic, highly dispersed fumed metal oxides which are produced by the high-temperature hydrolysis process. These metal oxides have special properties which can be extended by further chemical and/or physical after-treamtent.

Chemisorption
takes place when a gaseous, liquid, or dissolved material is added or absorbed at the surface of a solid or by a liquid with the formation of a chemical compound.

Affinity
The more heat is given off by the combining of two elements or compounds, the greater are the forces of attraction (affinity) between them (THOMSON-BERTHELOT principle).

Chromatography
Designation for a physical separation process during which the separation of materials takes place through distribution between a stationary and a mobile phase.



Coesite
SiO2 high-pressure modification. Detected as natural mineral in the sandstone of meteor craters.

Dipole interaction
Forces which act due to the presence of dispoles.

Dispersion
Uniform distribution of pulverulent materials in liquid systems with the aid of dispersing machines.

Convection
Movements of entire masses of liquids or gases, usually caused by temperature differences.

Doping
Designation common in semiconductor technology for the deliberate contamination of ultrapure germanium and silicon crystals by additions of tiny amounts of foreign material.

Coordinative defect point

An atom which does not reach the normal coordination number; i.e. the number of the adjacent (atomic) neighbours is reduced.

Cristobalite
is the modification of silicon dioxide stable above 1470C up to the melting point of quartz (1710C). Forms small, cloudy, milkywhite crystallites on cavities in vulcanic rocks.

Educt
Starting material for a chemical reaction.

EINECS
Abbreviation of European Inventory of Existing Chemical Substances. In these material lists, the registered products are arranged according to EINECS and CAS numbers.

Crystalline
is the term used for solids whose structural elements are arranged in regular crystal lattices. Opposite: amorphous.

Emulsion
Thermodynamically more or less instable systems which contain two liquids only slightly soluble in each other in a finely divided state.

Devitrification
Change from a vitreous condition. Spontaneous crystallization of an amorphous substance.

Differential thermal analysis

Thermometric method of analysis. Makes it possible to observe phase changes on the basis of their heat tonality, and is suitable above all for studies of structural changes in solid materials at higher temperatures.

Extinction
From the Latin: extinctio = extinction, quenching. Term used for the logarithm of the quotient of the primary beam intensity related to the intensity of the test beam.

Filter dust
Develops primarily in power plants as a by-product containing silica, flue dust.

Diffraction rings
X-ray diffraction.

Diffusion
Without the influence of external forces, a gradual mixing of different gaseous, liquid, or solid materials

Flame hydrolysis
Reaction in the flame of, for example silicon tetrachloride with the water formed in the oxyhydrogen flame.

Diglyme
Acronym for Diethylene glycol dimethyl ether, a solvent.

Flue dust
By-product containing silica which develops on an uncontrolled basis during the production of silicon or ferrosilicon. Physiologically in contrast with deliberately-produced silicas not harmless. As synonym, the expression flue ashes is also used.

Dipole
Asymmetrical distribution of charge in the case of molecules.



Frozen section
Section of a frozen test specimen and study of the section surface, for example, for the degree of dispersion of fillers.

Homogeneous
Identical in type, nature, and material.

Hydrogen bridge linkage

Designation for a bond which forms between a hydrogen atom covalently bonded to electronegative elements ( proton donor) and the sole electron pair of another electronegative atom ( proton acceptor).

Fused silica
Turbid, non-transparent silica glass which is not suitable for optical purposes.

GC/MS coupling
Separation of a gas mixture by gas chromatography ( chromatography), and identification by mass spectrometry.

Hydrophilic
Water-attractive or water-wettable. Opposite: hydrophobic.

Geminal
expresses the situation that two substituents are bonded with the same atom, vicinal.

Hydrophobic
Water-repellent. Opposite: hydrophilic.

Gravitational interaction
Forces which two bodies exert on each other due to their mass (at small mass: weak interaction).

Inert
Inactive, non-reactive.

Infrared (IR) spectroscopy

Modern optical process, in which the absorption spectra of usually organic, solid, liquid, or gaseous compounds are used in the infrared range for qualitative and/or quantitative analysis, structure determination, and similar studies.

Half width
Peak width at half the maximum peak amplitude.

Handling
Measures and processing methods necessary to realize certain operating sequences, above all with pulverulent raw materials, while observing officially-specified guide or limit values.

Interference
Phenomena which result from the superimposition of waves of the same wavelength.

Headspace analysis
Name given to a method of analysis, usually conducted by means of gas chromatography ( chromatography), of the air space (headspace) above a solid or a liquid.

Intermolecular
Designation for all processes or forces which take place or act between several similar or dissimilar atoms or molecules. Opposite: intramolecular.

Hexagonal
Designation for a crystal system which occurs in the form of small six-cornered columns or in rhombohedrons.

Intramolecular
Designation for all processes or forces which take place or act within the individual molecules. Opposite: intermolecular.

Highly dispersed
very finely divided.

Irreversible
Chemical reaction which can not be made to take place in the opposite direction. Opposite: reversible.

High-temperature form
Modification which is readily formed at higher temperatures.



Kieselguhr
Synonym for infusorial earth, diatomaceous earth. Very finegrained, light-weight, usually light gray powder which consists of 70 -90 % -x amorphous silica, some percent of crystalline silica, 3-12 % water, and slight amounts of organic admixtures.

Orbital interactions
Domiciles of the electrons of atoms or molecules come very close to each other or overlap; in such a case energy can be released (stable state).

Phases
Designation for the different crystalline forms in which a pure chemical substance can occur.

LSR system
Abbreviation for Liquid Silicons Rubber = liquid silicone systems which usually become addition cross-linked in the presence of a platinum catalyst.

Plasma process
One of the possible production processes leading to pyrogenic silicas by means of ionized gases.

MAK value
Abbreviation for maximale Arbeitsplatz-Konzentration (Maximum concentration at the work place). Highest permissible concentration of a working material in the air at the work place.

Pneumoconiosis
Medical term for the illness commonly known as dust on the lung.

Modification
Various forms of state of chemical elements or compounds with the same composition but different physical characteristics.

Precipitated silicas
Largely nonporous, synthetic silicas which develop during the conversion of water glass with sulphuric acid.

Morphology
Science of the development and origin of forms and shapes.

Primary particles
According to DIN 53206, the smallest particles (individual particles) which make up powdered solids. Particle recognizable as an individual by means of electron microscopy.

Nanometer
One millionth of a millimeter = 1 nm.

Neutron activation
Highly sensitive process for trace analysis; in this process a sample of a substance is bombarded with neutrons. The partiallyformed radioactive isotopes are used for the characterization.

Progessive
Advancing.

Proton acceptor
Compounds which can accept protons (H+ ions) (according to BRNSTED = bases). Opposite: proton donor.

NMR
Abbreviation for Nuclear Magnetic Resonance. Spectroscopic process to provide information on the structure of chemical substances.

Proton donor
Compounds wich can give off protons (H+ ions) (according to BRNSTED = acids). Opposite: proton acceptor.

Octet rule
Describes the efforts of atoms to attain eight electrons in the outer electron shell (precious gas configuration) by means of chemical bonding.

PU systems
Abbreviation for polyurethane systems.



Pyrogenic
Generated in the flame.

SEM
Abbreviation for scanning electron micrograph.

Quartz
Most important crystalline modification of SiO2. Most frequently occurring mineral in the earths crust. Mainly colourless, white, glassy or greasy-looking, opaque milky or transparent crystal druses

Short-range order
Almost regular regions of an otherwise amorphous substance.

Silanes
are, in the narrower sense, binary compounds of silicon with hydrogen, and with the general formula SinH2n + 2 are, in other words, the Si equivalents of the alkanes. The term is also used in the wider sense for such derivatives in which the hydrogen atoms are partially or even completely replaced by other groups.

Quartz glass
Completly transparent, clear glass which only melts at 1,720C and has a high chemical resistance.

Reversible
A chemical reaction which can be made to take place in the opposite direction. Opposite: irreversible.

Silanol groups
Groups on the silica surface represented by the formula = Si-OH.

Rheology
Science of flow. Subdivision of physics which deals with the description, explanation, as well as the measurement of phenomena occuring in bodies when they are subjected to deformation.

Silica
Collective term for compounds with the general formula SiO2. We distinguish, for example, between pyrogenic, e. g. AEROSIL fumed silica and precipitated silicas. The individual types of silica differ from each other in their physical-chemical properties, for example size of the specific surface, particle size, as well as drying and ignition losses. silica gel, arc silica.

Rhombohedron
A crystal bounded by six rhombic surfaces with four corners.

Silica gel
Porous silica produced according to the wet process from acid and water glass. Opposite: precipitated silica.

Rock crystal
is an especially pure, glass-like, transparent form of quartz. It often forms impressive, trapezohedral-hemihedral, individual crystals.

Silicone rubber
Highly viscous silicone oils which can be cross-linked to elastomers with peroxides or according to other principles. The basic polymer for silicone rubber is dimethylpolysiloxane.

Rotor-stator machine
Also known as mixing siren. Machine for the dividing of a pigment or filler, consisting of an outer, fixed ring and an inner, concentric, rotating ring, whereby both rings have openings (holes or slots) which the liquid must pass through under high shearing stress.

Silicosis
progressive pneumoconiosis as the result of inhaling dust containing quartz: occupational disease.

Scarification
Superficial scratching of the skin without bleeding.

Siloxane groups
Si-O-Si units which develop as a result of the condensation of silanol groups.

Sedimentation
Settling behavior.



Specific surface
is according to DIN 66 131, the surface area of a solid material referred to the mass in m /g. It is generally determined according
2

Tridymite
high-temperature form of SiO2. Often six-sided flakes 1 - 4 mm in size, colourless, with vitreous lustre or milky turbid, transparent to translucent. modification of silica.

to the BET Method.

status nascendi
State of the origination. Reactive state of materials at the instant of their formation.

Tunnel effect
Atomic particles can overcome a potential barrier, the potential energy of which is higher than the kinetic energy of the particles, with a certain probability by employing a so-called tunneling through.

Stishovite
Very hard SiO2 mineral insensitive to shock. Develops at points of impact of larger meteorites due to the powerful shock wave from the quartz grains embedded in the ground. The silicon atom is not surrounded by four O atoms, as is the case with usual SiO2, but instead by six equidistant O atoms. Stishovite can also be produced synthetically under extremely high pressures.

UP systems
Abbreviated name for unsaturated polyester resins.

Vicinal
describes the position of the substituents at adjacent atoms. geminal.

TEM
Abbreviation for transmission electron micrograph.

Viscosity
is, according to DIN 13 342, the characteristic of a material to absorb, through tangential deformation, a tangential stress that depends on the velocity gradient.

Tetragonal
The four bonding electron pairs point into the corners of a tetrahedron in the case of the tetragonal system, and consequently are spaced at the greatest possible distance from each other (angle about 109).

X-ray amorphousness
Property of substances which show no defined diffraction phenomena in the X-ray structural study.

Tetrahedron
Body limited by four equilateral triangles.

X-ray analysis
Physical process for the chemical analysis during which the test sample is irradiated with X-rays.

Thixotropy
Decrease in the viscosity of a liquid as a function of the shearing intensity and shearing duration, and readjustment to the original state after termination of the shearing stress.

X-ray diffraction
Process of crystalline structure analysis during which X-rays are diffracted at the electrons in the lattice atoms. Through superimposition of the diffraction waves, regular diffraction rings are developed.

Toxicology
Science of the harmful, under certain circumstances lethal, effects of substances in excessive amounts.

X-rays Tribo-electricity
Frictional electricity. Designation for the development of voltage when two different insulators are rubbed against each other and they become charged with opposite electrical signs. Often characterized as the quotient of charge per mass. Designation for a short-wave electromagnetic wave radiation of about 10 -6 to 10 -12 cm wave length.



Physico-Chemical Data of AEROSIL Fumed Silica

Hydrophilic AEROSIL Fumed Silica
Standard Grades
Test method Behavior with respect to water Appearance BET-Surface Area
1)


Special Grades

AEROSIL AEROSIL AEROSIL AEROSIL AEROSIL AEROSIL AEROSIL AEROSIL AEROSIL AEROSIL AEROSIL AEROXIDE AEROXIDE AEROXIDE Alu C TiO2 P 25 TiO2 PF 2 90 130 150 200 300 380 OX 50 TT 600 MOX 80 MOX 170 COK 84

hydrophilic fluffy white powder

m /g 9015 13025 15015 20025 30030 38030 5015 20050 8020 17030 18530 10015 5015 57.512

Average Primary Particle Size nm Tapped Density

2)

20

16

14

12

40

40

30

15

13

21

standard material

g/l

80 120

50 120

50

50

50

50 120

130

60

60

50

50

50

130

80

compacted material (V) g/l compacted material (VV) g/l

Moisture 3)

120 120 120 50/75 50/75/ 50/75/ 120 120 1.5 2

( 2 hours at 105 C ) at leaving plant site

Ignition Loss 4) 7)

wt. % wt. %

1.0 1

1.5 0.5 9) 1.5 1 1 1

2.0 2.5

1.5 1

2.5 1.5 2.5 1

1.5 1.5 1 1

5.0 1.5 2.0 3 2 3

( 2 hours at 1000 C )
pH Value 5) SiO2
8)

3.7-4.7 3.7-4.7 3.7-4.7 3.7-4.7 3.7-4.7 3.7-4.7 3.8-4.8 3.6-4.5 3.6-4.5 3.6-4.5 3.6-4.3 4.5-5.5 3.5-4.5 3.5-4.5 wt. % 99.8 wt. % 0.05 99.8 0.05 99.8 0.05 99.8 99.8 0.05 0.05 99.8 99.8 99.8 98.3 98.3 82-86 0.1 0.2 1-3

Al2O3 8) Fe2O3 TiO2 8) HCl 8) 10)

6) 8)

0.05 0.08 0.05 0.3-1.3 0.3-1.3 14-18 99.6 0.3 0.2 0.01

wt. % 0.003 0.003 0.003 0.003 0.003 0.003 0.01 0.003 0.01 0.01 0.1 wt. % 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03

0.1 99.5 94.0 0.5 0.3 0.8 10

wt. % 0.025 0.025 0.025 0.025 0.025 0.025 0.025 0.025 0.025 0.025 0.1 0.05 10 0.05 10 0.05 10 0.05 0.05 10 10 0.05 10 0.2 10 0.05 0.1 10 10 0.1 10 0.1 10

Sieve residue wt. % (according to Mocker, 45 m) Packaging (net/weight)

11)

0.05 0.05 10 10

kg

The data have no binding force. 3) 4) 5) 6) 7) 8) 9)

1) 2)

in acc. to DIN 66131 in acc. to DIN EN ISO 787/11, JIS K 5101/18 (not sieved) in acc. to DIN EN ISO787/2, ASTM D 280, JIS K 5101/21 in acc. to DIN EN ISO 3262-20, ASTM D 1208, JIS K 5101/23 in acc. to DIN EN ISO 787/9, ASTM D 1208, JIS K 5101/24 in acc. to DIN EN ISO 787/18, JIS K 5101/20 based on material dried for 2 hour at 105 C based on material ignited for 2 hours at 1000 C special moisture-protective packaging 10) HCl-content is part of the ignition loss 11) AEROSIL V-Grades will be delivered in paperbags of 20 kg 12) AEROSIL VV-Grades are presently only available from the production plant in Rheinfelden by now



Hydrophobic AEROSIL Fumed Silica

Test method Behavior with respect to water Appearance BET-Surface Area
1)

AEROSIL R 972

AEROSIL R 974

AEROSIL R 202

AEROSIL R 805

AEROSIL R 812

AEROSIL R 812 S

AEROSIL R 104

AEROSIL R 106

AEROSIL R 8200

AEROSIL AEROXIDE TiO2 T 805 R 816

hydrophobic fluffy white powder



m /g

11020 17020 10020 15025 26030 22025 16 50 90 12 50 90 60/90 13) 60/90 13) 60/90 13) 0.5 2 0.5 2 0.5 4-6 0.5 5-7 0.5 90 13) 0.5 14 50 12 50 7 50 7 50

15025 25030 16025 19020 12 50 90 7 50 140 12 40

4510 21 200

Average Primary Particle Size nm Tapped Density

2)

standard material

g/l

compacted material (V) g/l compacted material (VV) g/l

Moisture
3)

( 2 hours at 105 C ) at leaving plant site

Ignition Loss 4) 7)

wt. % wt. %

0.5

1.0

1.0 5.0

( 2 hours at 1000 C )
C-Content pH Value SiO2 8) Al2O3 Fe2O3 TiO2
8) 8) 5) 10)

1.0 - 2.5 1.5 - 3.0

1.0 - 2.5 1.0 - 2.5 2.5 - 3.5 2.0 - 4.0

wt. % 0.6 - 1.2 0.7 - 1.3 3.5 - 5.0 4.5 - 6.5 2.0 - 3.0 3.0 - 4.0 3.6 - 4.4 3.7 - 4.7 wt. % wt. % wt. % wt. % wt. %
12)

1.0 - 2.0 1.5 - 3.0 2.0 - 4.0 1.2 - 2.2 2.7 - 3.7 4.0 99.8 0.05 0.01 0.03 0.02 10 3.7 99.8 0.05 0.01 0.03 5.0 99.8 0.05 0.01 0.03 4.0 - 5.5 3.0 - 4.0 99.8 0.05 0.01 0.010 0.03 97.00 2.500

4-6 99.8 0.05 0.01 0.03

3.5 - 5.5 5.5 - 7.5 5.5 - 7.5 99.8 0.05 0.01 0.03 99.8 0.05 0.01 0.03 0.025 10 99.8 0.05 0.01 0.03 0.025 10

99.8 0.05 0.01 0.03 0.05 10

99.8 0.05 0.01 0.03 0.1 10

8)

HCl 11) Packaging (net/weight)

0.025 0.025 10 10

0.025 0.025 0.025 10 15 10 20

kg

The data have no binding force. 4) 5) 7) 8)

1) 2) 3)

in acc. to DIN 66131 in acc. to DIN EN ISO 787/11, JIS K 5101/18 (not sieved) in acc. to DIN EN ISO 787/2, ASTM D 280, JIS K 5101/21 in acc. to DIN EN ISO 3262-20, ASTM D 1208, JIS K 5101/23 in acc. to DIN EN ISO 787/9, ASTM D 1208, JIS K 5101/24 based on material dried for 2 hour at 105 C based on material ignited for 2 hours at 1000 C 10) in Water: methanol = 1 : 1 11) HCl content is part of the ignition loss 12) AEROSIL V-Grades will be delivered in paperbags of 15 kg 13) AEROSIL VV-Grades will be delivered in paperbags of 15 kg



The information and statements contained herein are provided free of charge. They are believed to be accurate at the time of publication, but Degussa makes no warranty with respect thereto, including but not limited to any results to be obtained or the infringement of any proprietary rights.

Use or application of such information or statements is at users sole discretion, without any liability on the part of Degussa. Nothing herein shall be constructed as a license of or recommendation for use which infringes upon any proprietary rights. All sales are subject to Degussas General Conditions of Sale and Delivery.

0



Contact
Degussa AG Business Line Aerosil Weissfrauenstrasse 9 D-60287 Frankfurt am Main, Germany Phone: +49 69/218-2532 Fax: +49 69/218-2533 E-Mail: aerosil@degussa.com http: //www.aerosil.com

Technical Service
Degussa AG Technical Service Aerosil Rodenbacher Chaussee 4 P. O. Box 1345 D-63403 Hanau-WoIfgang, Germany Phone: +49 6181/59-3936 Fax: +49 6181/59-4489

NAFTA
Degussa Corporation Business Line Aerosil 379 Interpace Parkway, P. O. Box 677 Parsippany, NJ 07054-0677 Phone: +1 (800) AEROSIL Phone: +1 (973) 541-8510 Fax: +1 (973) 541-8501

NAFTA
Degussa Corporation Technical Service Aerosil 2 Turner Place Piscataway, NJ 08855-0365 Phone: +1 (888) SILICAS Phone: +1 (732) 981-5000 Fax: +1 (732) 981-5275

Asia (without Japan)

AEROSIL Asia Marketing Office c/o NIPPON AEROSIL CO., LTD. P. O. Box 7015 Shinjuku Monolith 13F 3-1, Nishi-Shinjuku 2-chome Shinjuku-ku, Tokyo 163-0913 Japan Phone: +81-3-3342-1786 Fax: +81-3-3342-1761

Asia (without Japan)

Degussa AG Technical Service Aerosil Rodenbacher Chaussee 4 P. O. Box 1345 D-63403 Hanau-WoIfgang, Germany Phone: +49 6181/59-3936 Fax: +49 6181/59-4489

Japan
NIPPON AEROSIL CO., LTD. Sales & Marketing Division P. O. Box 7015 Shinjuku Monolith 13F 3-1, Nishi-Shinjuku 2-chome Shinjuku-ku, Tokyo 163-0913 Japan Phone: +81-3-3342-1763 Fax: +81-3-3342-1772 please visit our web site www.aerosil.com to find your local contact partner

Japan
NIPPON AEROSIL CO., LTD. Applied Technology Service 3 Mita-cho Yokkaichi, Mie 510-0841 Japan Phone: +81-593-45-5270 Fax: +81-593-46-4657
TB 0011-1-Apr06