The Institute of Energy's Second International Conference on CERAMICS IN ENERGY APPLICATIONS: Proceedings of the Institute of Energy Conference Held in London, UK, on 20-21 April 1994

(Hons)

Chapter 1

New Developments & Applications

Outline

Chapter 1: MANUFACTURE AND EVALUATION OF HIGHLY POROUS CERAMICS WITH ADJUSTABLE ELECTRICAL RESISTANCE

Chapter 2: Si3N4-Si COMPOSITE CERAMICS AND CHEMICALLY TOUGHENED SiC FOR ENGINE COMPONENTS

Chapter 3: BETTER CERAMICS THROUGH MICROWAVES

Chapter 4: MICROWAVE-ASSISTED FIRING OF CERAMICS

MANUFACTURE AND EVALUATION OF HIGHLY POROUS CERAMICS WITH ADJUSTABLE ELECTRICAL RESISTANCE

F.J. Dias, M. Kampel, F.J. Koch and H. Nickel,     Forschungszentrum Jülich GmbH, Institut für Werkstoffe der Energietechnik, 52425 Jülich, Germany

ABSTRACT

Ceramic powders are first coated with a synthetic resin by a special coating procedure, the Coat-Mix procedure, and granulated. Shaped bodies from the granular material show after the subsequent heat treatment a high continuous porosity, a considerable specific surface and an excellent thermal shock resistance. Appropiate starting powder combinations and doping measures allow to adjust the materials specific electrical resistivity between 10−2 ω cm and 10⁴ ω cm.Engineering components of this material are highly efficient filters which can be heated to temperatures up to 1000°C and more by direct current flow in the low voltage range. They are thus particularly suitable for use as soot filters, filters and heat exchangers for gases and some liquids, heatable catalyst supports and porous ceramic electrodes for chemical process engineering.

INTRODUCTION

Ceramic materials manufactured using the coat-mix (CM) technique [1] are especially characterized by extreme thermal cycling resistance and high continuous porosity [2]. Further chemical and physical properties of these materials can be selectively produced by the application of suitable starting materials and adequate measures in the manufacturing process. The Institute for Materials in Energy Systems of the Research Centre, Jülich has developed a highly porous ceramic base material of silicon carbide whose specific electrical resistance can be adjusted by doping with suitable impurities so that flow heater elements (DFH) made of this material are heatable to temperatures > 1000°C at a voltage below 50 V in spite of high porosity [3]. Thanks to their chemical and thermal resistance, good retention capability for dust or soot particles and high permeability to gases and liquids, these heater elements can be used both as electrically regenerative diesel soot filters and as filters and/or heat exchangers for various liquid or gaseous media.

1 MANUFACTURE OF DFH BASED ON THE CM TECHNIQUE

1.1 Coating of the Filler Powders with Synthetic Resin Binder According to the CM Technique

A synthetic resin of the Novolac type is first of all dissolved in alcohol by heating to 50 – 60°C. A resin concentration between 5 % and 35 % is selected for this solution depending on the composition and specific surface of the filler to be coated and the finished product properties aimed at.

This hot binder solution is then mixed with the corresponding amount of filler material (Si, SiC, C powder and possible doping agents) by vigorous stirring, and the cooled viscous suspension is then injected into cold water by means of a mixing nozzle. In this process, the previously dissolved binder resin is redeposited as a very fine precipitate on the filler grains coating them with a homogeneous binder envelope which initially still contains solvent residues. These are removed by heating the aqueous suspension to approx. 40°C, while stirring it, followed by cooling to room temperature after a short hold time. The coated filler material is then separated from the liquid phase by decantation and filtration and finally dried.

Attention must be paid during drying to ensure that the still wet filter cake is not heated above 50°C, since it would otherwise agglomerate by premature clotting of the individual grains. Drying is therefore carried out in a vacuum dryer [4].

1.2 Granulation and Shaping

The flowable CM powders coated with binder consist of tiny agglomerates in which both the individual filler components and the doping agents are homogeneously distributed. In order to mould coarse-pored bodies from these CM powders, pellets [5] of up to 2 mm diameter are produced and classified.

Depending on the desired permeability, moulds are produced from the CM powders or from suitable pellet fractions by die-pressing (plates) or semi-isostatic pressing (tubes). This is done by heating the pellets or CM powders to 120 – 140°C in appropriate shaping devices and compressing them to green bodies at forming pressures between 150 mbar and 10 bar. In this way, it is also possible to produce shaped bodies with zones or layers of defined pore structure and electrical resistance by using adequate pellet fractions with corresponding doping agents in these locations.

1.3 Coking

The green bodies are subsequently heated up to 850°C in slowly flowing inert gas (argon), which causes the binder resin to be pyrolysed leaving a coke residue. This binder coke together with the initial filler carbon is now present at a molar ratio of about 1:1 to the silicon also used as a filler.

The as-coked specimens can be easily machined to size.

1.4 Siliconizing

The last process step is siliconizing. This is done by subjecting the coked and possibly machined components to a further thermal treatment in flowing Ar or N2 up to approx. 2000°C. The free silicon and carbon elements react with each other forming ß-SiC which now forms connecting bridges between the initially used α-SiC and pellet grains of the components. Fig. 1 shows the individual process steps of manufacture.

Fig. 1 Production of CM-SiC ceramic

2 MODE OF OPERATION AND PROPERTIES OF DFH

Technical applications use primarily tubular filter heaters with electrodes at the ends. Several such elements can be connected in parallel or in series and heated to operating temperature by either direct or alternating current. The working medium to be cleaned or heated (gas, oil, paraffin etc.) flows radially from the outside through the pore system of the filter tube closed at one end (Fig. 2) and leaves the tube through the open end in a cleaned or tempered state. The reverse direction of flow is also possible. Depending on the application purpose, heating can be periodic or continuous. In the case of diesel soot filtration, for example, the filter can be regenerated upon reaching a critical differential pressure by periodic combustion of the deposited soot. When used as a heat exchanger, an DFH with an effective length of only 23 cm and an open porosity of 66 % provides a contact surface of about 2 m² for heat exchange, so that a gentle and effective heat transfer can be ensured.

Fig. 2 Cross section of a tubular filter heater element (DFH)

2.1 Physical Properties

As shown in Table 1, the application-related physical properties of this material can be adjusted within a fairly large range. As an electrically conducting, highly porous ceramic material, however, its filtering properties and electrical resistance are of decisive significance.

Tab. 1

Technical data variation range of SiC-based CM ceramics

2.1.1 Filtering properties

Permeability, flow resistance and retention capability are the most important filtration features of an DFH. They are determined by the pore structure of the material, whose total porosity can be varied between 20 and 70 %. Fig. 3 and Fig. 4 show that, in addition to a fine porosity (10–200 µm) in the pellets, the material also exhibits a coarse porosity (100–1000 µm) that is formed between the pellet boundaries and substantially determines the filtering properties. The fraction and structure of this porosity can be adjusted by suitably selecting the pellet size and varying the forming pressure within a wide range. In this way, filters of identical geometry were produced whose permeability to air ranged from a few cm³ · dm–2 · min–1 to a few m³ · dm–2 · min–2 at the same differential pressure. Fig. 5 shows the permeability to air of an DFH used as a diesel soot filter as a function of differential pressure for different application phases. Further technical data of this filter element are compiled in Table 2.

Tab. 2

Technical data of a typical SiC-DFH

Fig. 3 Single pellet of CM-SiC

Fig 4 Polished section of a DFH showing its pore structure

Fig. 5 Air permeability of a CM-SiC diesel soot filter as function of differential pressure at different operating phases

2.1.2 Adjustment of electric resistance

The resistivity of self-bonded high-density technical silicon carbide bodies ranges from 10³ to 10⁶ Ω cm [6] and increases exponentially with growing porosity. However, the resistance of these bodies can be significantly increased or reduced by the incorporation of suitable impurities in the SiC lattice (doping) [7, 8, 9]. For example, conventional high-density SiC bodies can by adeaquate doping be produced both as high-resistance (10¹³ - 10¹⁴ Ω cm) electric insulators [7] and as low-resistance conductors [8, 9] in the resistance range from 10−3 to 10−3 Ω cm.

In order to ensure that an DFH, which is a heater element of technical dimensions made from highly porous CM-SiC ceramics, can reach the envisaged application temperature in the low-voltage range (up to 50 V), its overall resistance must be adjusted in relation to its geometry. In the case of an DFH whose geometry is shown in Fig. 2 and which can be used, for example, as a soot filter, the required resistance is achieved by doping with nitrogen. This is done by injecting N2 or N2-containing argon into the reaction space during the siliconizing step (section 1.4), i.e. during the formation of ß-SiC. This nitrogen is then rapidly incorporated into the microstructure in such a way that silicon atoms are partially replaced by nitrogen atoms in the lattice. The electrical conductivity of the SiC is thus substantially increased by the generation of one conduction electron per incorporated nitrogen atom.

This method therefore rapidly leads to doping levels which cannot be achieved, or only in a lengthy process, by the usual subsequent nitrogen treatment. Fig. 6 shows the dependence of the material’s electric resistance on N2 concentration during siliconizing. It can be seen that no further increase in SiC conductivity is achieved above an N2 concentration of approx. 15 %. This is due to the limited solubility of nitrogen in the SiC lattice.

Fig. 6 Influence of the nitrogen concentration of the furnace on the electrical resistance of CM-DFH

In order to establish further possibilities of adjusting the resistance of the DFH, the CM material was doped with the elements aluminum, boron and antimony [10]. For this purpose, small amounts of finely powdered doping agents were added to the filler mixture and coated jointly (section 1.1). The bodies produced from these pre-doped CM powders or from their pellets with 1 wt.% doping agent each exhibited different temperature-dependent resistances after siliconizing in Ar, as expected (Fig. 7). If this pre-doped body is siliconized in however, the generated resistivities are different from those of the material doped only with nitrogen.

Fig. 7 Range and temperature dependent specific ohmic resistance of differently pre-doped CM-SiC specimens siliconized in argon

As expected, the conduction electrons produced by nitrogen are compensated by those produced by aluminum and boron, both of which produce holes when incorporated into the crystal lattice of SiC, so that the resistance is increased.

In contrast, a further reduction in electrical resistance was achieved by antimony, which generates conduction electrons in the same way as nitrogen. It was thus possible to additionally incorporate impurities acting as donors in the SiC lattice beyond the solubility of nitrogen (Fig. 8).

Fig. 8 Range and temperature dependent specific ohmic resistance of differently pre-doped CM-SiC specimens siliconized in nitrogen

As already mentioned in section 1.2, differently pre-doped CM powders or pellets from such powders can also be used to produce composites exhibiting higher or lower resistance at selected locations (zones, layers). Adequate doping combinations may lead, for example, to composites which generate only one burning layer or several burning zones during current flow.

2.2 Chemical Properties

Since the DFHs described above essentially consist of silicon carbide, they are chemically resistant to almost any of the usual gases and liquids even at elevated temperatures. Above 750°C, however, silicon carbide is increasingly oxidized according to the reaction

The SiO2 thus formed causes a weight increase of the specimens, which can be used as a measure of the degree of oxidation.

In order to study the oxidation behaviour of the DFH which can also be used in oxidizing atmosphere up to 800°C, long-time corrosion tests were carried out in air at temperatures of up to 1000°C [10, 11].

Exposure tests with undoped filter material at 1000°C in dry air for 1350 h did not result in poorer filtration properties or reduced mechanical strength despite a 7 % weight increase [11].

Experiments with N-doped specimens, which were also oxidized in air, showed (Fig. 9) that oxidation only slightly increased the electric resistance of the material [10].

Fig. 9 Influence of the oxidation grade on the electric resistance of N-doped CM-SiC

It was furthermore found that the differently doped filter materials exhibited different oxidation behaviour under identical oxidation conditions (Fig. 10).

Fig. 10 Oxidation behavior in air at 950 °C of differently doped CM-SiC specimens

REFERENCES

1. H. Luhleich, F.J. Dias, P. Pflaum, H. Nickel, Das Coat-Mix-Verfahren, KFA-Bericht Jül 1221

2. H. Nickel, F. J. Dias, K. Bach, W. Best, W. Simonis, Entwicklung von Heiß gasfilter aus SiC auf Basis des Coat-Mix-Verfahrens, 2. Symp. Material forschung 1991, Dresden, Germany

3. Dias, F. J., Koch, F. J., Kampel, M., Nickel, H. Low voltage heatable highly porous ceramic filters. Proceed. Third Euro-Ceramics. Sept. 1993; V. 3:1107–1112. [Madrid].

4. H. Luhleich, F.J. Dias, P. Pflaum, W. Hannen, Vacuum drying process, Technische Information Nr. 22, KFA Jülich, April 1979

5. K.M. Röttgers, Herstellung kugelförmiger Teilchen aus binderbeschichteten Pulvern, Diplomarbeit, FH Aachen, 1986

6. Rubisch, O., Schmitt, R. Eigenschaften von SiC-Körpern verschiedener Dichte. Ber. Dtsch. Keram. Ges. 43, 1966.

7. Maeda, K. Effects of carrier concentration on electrical resistivity of SiC ceramics with BeO addition. J. Ceram. Soc. Jpn., Inter. Ed. 1989; 97:722–728.

8. Gnesin, G. G., Shipilova, L. A., Kasyanenko, A. A. Electrical conductivity of self-bonded SiC doped with Boron. Sov. Powder Metal, and Met. Cer. 22(no. 12), Dec. 1983.

9. Gnesin, G. G., Zakharenkov, V. K., Shipilova, L. A. Volume electrical resistivity of SiC heating elements. Sov. Powder Metal, and Met. Cer. 17, 1978.

10. F.J. Koch, Untersuchungen zur Beeinflussung des elektrischen Widerstandes von hochporösem Siliciumcarbid, Diplomarbeit, FH Aachen, 1993

11. Ahladas, P., Dias, F. J., Naoumidis, A., Nickel, H. Oxidation behaviour of CM-SiC Filters. Proceed. Third Euro-Ceramics. Sept. 1993; V.3:961–966. [Madrid].

Si3N4-Si COMPOSITE CERAMICS AND CHEMICALLY TOUGHENED SiC FOR ENGINE COMPONENTS

V Vikulin, A Romashin and T Leshchuk,     Research and Production Enterprise Tekhnologiya, Obninsk, Russia

ABSTRACT

The possibility of increasing ceramics crack resistance by self re-inforcement of silicon matrix with the Si3N4 grains of the elongated structure is demonstrated on the basis of a new composite material of Si3N4-Si system. This composite ceramic material exhibits high mechanical properties: KIC is up to 8.5–10.0 MPa·m¹/², σbnd by room temperature is up to 580 MPa and σbnd by 1300°C is up to 420 MPa. It retains high resistance to oxidation and C-containing media. It is an electroconductive material.Rotor blades of this material have undergone tests on acceleration rig at 1050°C and rotational speed 12000–36000 revolutions per minute. Elements of cylinder-piston assembly for internal combustion engine have successfully undergone tests at 800–1200°CThe materials based on chemically toughened and composite silicon carbide possess high thermal vibration resistance and are intended for use in oxidizing atmosphere at temperatures up to 1600–1700°C. The characteristic feature of the technology developed lies in the fact that in case of linear shrinkage 0.5–0.3% the products after presintering can be easily machined with the conventional tools and the subsequent modification does not change their dimensions. The material withstands thermal shocks in gas flows with high temperature values.Nozzle blades of OTM-910 (material based on SiC) have undergone thermocyclic tests on gas-dynamic rig at gas flow temperature 1620°C with cooling down to the room temperature. Ceramic flame swirlers for the combustion chamber have undergone tests in the combustion chamber section and in gas-turbine engine at gas flow temperatures 1100–1400°C with 400 engine starts and cooling of injectors with fuel.

1 INTRODUCTION

A wide application of Si3N4- and SiC-based materials in engine manufacturing is limited by a number of factors. One of these factors is a low crack resistance of Si3N4 ceramics. Another one is a limited level of operating temperature not exceeding as a rule 1300–1400°C. This pertains equally to most SiC-based materials containing low-melting sintering additives. Dense SiC materials intended for use at higher temperatures work preferably at low heating rate and do not withstand thermal shocks.

New Si3N4-Si composite material is used to illustrate methods of crack resistance increase. These methods include:

• attainment of dense structure, elimination of pores and microcracks, prevention of oxide additives diffusion from ceramics during sintering;

• formation of self-reinforcing microstructure in the form of elongated grains of β-Si3N4 through dissolution-recrystallization processes;

• introduction of dispersions causing the increase of crack propagation resistance, relaxation of stresses and the enhancement of dislocations movement intensity;

• generation of compression stresses in ceramics which prevent crack propagation.

During the development of low-shrinkage and shrinkproof SiC-based materials with improved thermooxidative stability and operating temperature above 1500°C the following scientific principals have been realized:

• use of SiC powders of high purity;

• chemical toughening of presintered SiC;

• formation of composite structure and areas with different thermal conductivity;

• protection of porous ceramics from oxidation.

2 RESULTS AND DISCUSSION

2.1 Selfreinforced Si3N4-ceramics

Formation of dense selfreinforced microstructure of ceramics based on densified reaction-bonded silicon nitride (DRBSN) with elongated crystals of β-Si3N4 is an efficient method of increasing material crack resistance [1]. Another method of ceramic material fracture toughness increase is the introduction of dispersions of various materials into the matrix [2]. The combination of these two methods of crack resistance increase allows us to obtain composite material in Si3N4-Si-Y2O3-MgO system with stress intensity coefficient KIC=8.5-10.0 MPa·m¹/². Silicon grains uniformly distributed in Si3N4 were used as dispersions. In case of such microstructure favourable compression stresses occur as a result of different temperature coefficients of expansion of basic phase (Si3N4 and Si) which prevent crack propagation.

Si3N4-Si material was obtained by nitridation of raw silicon containing the additive increasing the rate of silicon-nitrogen reaction at 1000–1100°C and also containing sintering additives Y2O3 and MgO. Subsequent densification was carried out at 1750–1800°C and nitrogen pressure 0.13 MPa in the mixture silicon nitride, boron nitride and MgO additives.

Thermodynamical calculations of the system Si-Y2O3-MgO-Fe2O3-N2 within the temperature range 700–2230°C show that at the temperatures of ceramics sintering above 1600°C the formation of gaseous products SiO, Mg, Si is observed.

Simultaneously with this the diffusion of MgO from ceramics into the mixture and vice versa was observed. The presence of MgO in Si3N4-BN-MgO mixture prevents the diffusion of glass phase components from ceramics and also the formation of large pores and material delamination [3].

Mass fraction of free silicon after synthesis and after the densification is 10-15%; in this case material density after the densification at 1750-1800°C amounts to as much as 97% of theoretical density for given composition at the linear shrinkage not exceeding 5%(Fig. 2.1). Densification processes begin at 1450°C. At first the material is densified by a liquid-phase diffusion mechanism. As the temperature increases the mechanisms of dissolution-recrystalization of silicon nitride in liquid phase SiY2O3-MgO with the formation of hexagonal grains of β-Si3N4 begin to act. The density dependence of ultimate bending strength and stress intensity factor KICSi3N4-Si material are shown in Fig. 2.2.