Professional Documents
Culture Documents
207
A. R. BOCCACCINI?
Institute for Mechanics and Materials, University of California at San Diego, La Jolla,
CA 92093-0404, U.S.A.
(Received 5 November 1997; accepted 4 December 1997)
Abstract. In order to investigate a potential use for recycled speciality glasses (specifically those
containing hazardous elements), a processing route has been developed for the fabrication of metallic
fibre mat reinforced glass matrix composites. Commercially available 3-dimensional stainless steel
316L fibre mats were used as the metal reinforcement, and a borosilicate glass which had been used
previously in radiation experiments was used as the glass matrix. The fibre mats were infiltrated
with a commercially available silica sol using electrophoretic deposition (EPD), and the glass matrix
was laid in between infiltrated fibre mats prior to consolidation using uniaxial cold pressing. It was
found that composites with sufficient integrity could be obtained from this recycled waste glass after
sintering in air at 850 C for 1 h. The deposited silica remained amorphous at the processing temperature, providing a porous interface between the metallic reinforcement and the waste glass matrix.
The processing issues involved in composite fabrication, namely, the EPD infiltration parameters for
the silica sol, the quantity and subsequent effect of the impurities present in the waste glass, and the
densification of the composite material on sintering, have been discussed.
Key words: recycling, waste glass, composites, metal fibre reinforcement, electrophoretic deposition.
1. Introduction
The development of metal-reinforced glass matrix composites (GMCs) is a promising alternative to monolithic glasses for achieving structural materials combining
intermediate temperature capability, toughness and damage tolerance [16]. The
incorporation of the reinforcing metallic phase into the glass matrix provides the
glass-metal composite body with a degree of pseudoductility, preventing catastrophic crack growth by such mechanisms as plastic deformation, debonding, pull? On leave from: Technische Universitt Ilmenau, Fachgebiet Werkstoffkunde, D. 98689, Ilmenau, Germany.
208
out and crack bridging [58]. The main potential toughening characteristic imparted to a brittle matrix by a metallic second phase is the dissipation of energy
by plastic deformation [9, 10]. In order to exploit this toughening mechanism, the
best results are obtained when using continuous metal reinforcements, including
boundary networks [9], foils [10] or continuous fibres [47, 11], as there is forced
crack/secondary phase interaction in these cases. Examples of continuous ductile
metal reinforcements for glass matrix systems which have been studied to date
include: lead [7]; Ni [1]; Cu and Ni-Si-B alloys [4, 5] and stainless steel [11].
When considering continuous fibre reinforcement, however, the properties of the
composite material are invariably anisotropic, which can be a disadvantage. Recent advances in ceramic processing have attempted to alleviate the problem of
anisotropy by incorporating woven reinforcements into a matrix material [1214].
These 2D and 3D reinforcements reduce material property anisotropy and improve
the inter- and intra-laminar strengths. Apart from the present authors own recent
work [14], we are only aware of the work of Russian researchers who have used
2D metallic fibre mats to reinforce glasses [15]. Interest in these reinforcements
may increase due to the fact that, in recent years, more woven metallic fibres
have become available through their use in the production of anti-static/conductive
textiles and for the fabrication of filters [16]. Preliminary studies have been undertaken on the use of such woven fibres in the fabrication of a model glass matrix
composite [14] and this work has led to further research efforts being applied to the
development of GMCs, with particular emphasis being placed on the use of waste
glass for the matrix material.
The growing interest in ecological preservation has led to an increase in the
recovery of solid wastes, including glass cullet from the hollow and float glass
production processes as well as the silicate residues from combustion processes,
such as slag and flyash from coal power stations or incinerators [1719]. Besides
the traditional use of slag and flyash as a filler in the fabrication of cements [18],
alternative uses of the recovered silicates have been proposed including the fabrication of glass-ceramics with interesting mechanical properties [19, 20], or the use
of mixtures of cullet glass and flyash to form the matrix of particle reinforced glass
matrix composites [17]. In this context, the development of alternative techniques
to reuse (recycle) speciality glasses e.g. glasses from fluorescent tubes, TV-set
cones and screens, and cathode-ray tubes is of paramount importance because
such glasses cannot be directly re-used in the glass production plant via the melting
process [21]. This is due to the significant variation in their composition which
depends on the manufacturer, year of production, etc. In addition, many of these
glasses contain significant amounts of hazardous elements, e.g. heavy metals such
as Pb, Ba and Sr, which could be leached out by environmental factors, for example, whilst in contact with water, which would then lead to ecological pollution
when the glass cullet is buried in normal landfill sites [22]. Hence, in order to
overcome these drawbacks, new concepts are continuously sought to recycle these
speciality glasses by forming new products.
209
The successful implementation of such techniques will also act to reduce the
amount of cullet glass deposited in landfill sites, which is an unsatisfactory practice
both from an economical and ecological point of view. For glass residues containing heavy metals, techniques have been developed to reuse colour-mixed cullet
glass or waste glass from incinerators together with clays, to form composite materials [23]. Another approach suggested and experimentally verified has been the
fabrication of glass fibres from waste TV glass [24]. Recently, the development of
sintered products from Ba- and Pb-containing glasses was demonstrated also [25].
This approach exploits the low sintering temperatures of these glasses, allowing
for processing temperatures in the region of 650900 C. In the work here, a new
alternative is presented for the secondary recycling of speciality glasses, such as
those used in the manufacture of fluorescent tubing for radiation experiments [26].
The approach involves the use of such glasses as the matrix material for a metallic
woven fibre reinforced GMC. The metallic fibre mats were infiltrated with a silica
sol using electrophoretic deposition [1214] prior to composite manufacture, in
order to minimise intra-tow porosity. The main issues involved in the fabrication
of such composites are presented and it is envisaged they may find applications
as structural materials for low to moderate load bearing applications, provided the
environment where they are used guarantees a low leachability of the contaminant
elements they may contain.
2. Experimental
The metallic reinforcement used in this work comprised 316L stainless steel fibres
(14 m diameter) laid-up in a 3D labyrinth architecture and sintered to form a
durable, pleatable material (Bekipor ST, Bekitherm FA, Belgium). It was chosen,
on the basis of its suitability, to be infiltrated by sol particles using electrophoretic
deposition (EPD), as described below. The maximum use temperature in air for
this grade of stainless steel is 900 C and the thermal expansion coefficient (20
700 C) is 16.8 106 1/ C [27]. Due to this relatively low thermal capability and
the oxidation resistance of the metallic fibre used, one must ensure that any glass
material used for the matrix can be consolidated at temperatures of (or below)
900 C. The waste glass used was predominantly a borosilicate glass [26], which
had been recycled after use as fluorescent tubing in radiation experiments. The
density of the glass was measured as 2.19 g/cm3 and it was available as a powder with an average particle size of 25 m. Simultaneous differential thermal
analysis (DTA)/thermogravimetric analysis (TGA) was employed on the powder
using a Stanton-Redcroft STA 781 thermoanalyser to chart the possibility of crystallisation of phases. Dilatometry was also performed on pellets of matrix material
to ascertain the point of maximum rate of densification. The pellets used were dry
pressed uniaxially using a pressure of 300 MPa and each pellet had a diameter
of 12 mm and a height of 10 mm. From the dilatometry results, an optimum sintering temperature was ascertained and used subsequently to sinter pellets
210
of pure matrix. The matrix was then analysed by scanning electron microscopy
(SEM) using a JEOL 6300 scanning electron microscope in both secondary and
backscattered electron imaging modes. Any contaminant phases observed in the
glass matrix were analysed using electron energy dispersive X-ray analysis (EDX).
A commercially available silica sol (K342, Degussa Aerosil MOX80, Degussa Ltd,
Germany) was used for the electrophoretic infiltration of the fibre mats. This sol is
stable in the pH range 46, has a solids content of 42 wt.-% and the sol particles
are spherical with a broad particle size distribution (10100 nm) and an average
particle size of 30 nm. A dried sample of this powder was analysed using TGA to
asses the amount of expected weight loss at the composite sintering temperature.
The processing of the composites can be divided into two major steps: (i) infiltration of the reinforcement fibre mats and (ii) green body formation and composite
consolidation.
2.1.
211
as the anode in the EPD cell. Two stainless steel plates placed either side of the
fibre preform served as the negative electrodes. The silica particles migrated under
these conditions towards the metal fibre preform and infiltrated the labyrinth structure. Experiments were performed using varying applied voltages and deposition
times in order to find the optimum conditions for the complete infiltration of the
sol into the preforms. Infiltrated preforms were dried in air and then prepared for
examination via SEM using standard ceramographic techniques.
2.2.
The EPD-infiltrated fibre mats were used to prepare a glass matrix composite by
a simple uniaxial cold-pressing and sintering route. Typically, two fibre mats were
sandwiched between layers of the waste glass matrix powder in a die (24 mm diameter) to form the green bodies. The fabrication of similar laminated composites,
but using a model soda-lime glass as matrix, has been presented in an earlier report
[14]. Uniaxial pressures of 100 MPa were employed to obtain samples of sufficient
strength to be handled. The specimens were heated at a rate of 10 C/min up to the
sintering temperature ascertained from the dilatometry studies of the glass matrix,
and the dwell time at temperature was 1 h before furnace cooling. Selected sintered composite specimens were cut, polished and observed using SEM. Composite
consolidation by this simple, pressureless densification route was performed at this
stage to investigate the presence of any reaction at the silica/metal or the silica/glass
matrix interfaces and to assess whether pressureless sintering is capable of yielding
dense, i.e. porous-free, materials.
3. Results and Discussion
3.1.
MATRIX RESULTS
The graph in Figure 2 shows the dilatometry results for the matrix glass. The curve
shows that the rate of densification of the glass increases rapidly above 600 C and
reaches a maximum at 850 C. This maximum rate of densification temperature is
below the 900 C threshold of the stainless steel matrix and therefore this matrix
material can be feasibly used to fabricate stainless steel reinforced GMCs without
undue oxidation of the reinforcement. The XRD trace of this matrix in the temperature range 700 to 900 C is shown in Figure 3 and it shows that crystallinity of the
matrix begins at 800 C. In addition, with reference to the relative peak intensities,
it is evident that there is an increase in the level of crystallinity in this glass with
temperature. This increase in crystallinity reduces the propensity for the glass to
densify via viscous flow mechanisms. From the dilatometry result, however, it is
clear that although the glass begins to crystallise at 800 C, the extent of crystallinity
at this temperature does not significantly hinder the matrix densification process.
The optimum sintering temperature of 850 C attained from dilatometry and
XRD was used subsequently to sinter a powder compact of the matrix material.
212
Figure 2. Graph of the dilatometry results for the waste glass matrix showing a maximum rate
of densification at 850 C.
213
Figure 3. X-ray diffraction traces of the waste glass matrix showing the onset of crystallisation
of the glass to silicate hydrate (SiO2 xH2 O) at 800 C.
214
(a)
(b)
Figure 4. (a) A backscattered electron micrograph of the waste glass material. Note the presence matrix cracks and regularly-shaped impurities (in white) distributed evenly throughout
the matrix. (b) EDX analysis trace for one such impurity, showing it to be gadolinium-based.
215
Figure 6. A DTA/TGA trace for the K342 silica sol used to infiltrate the fibre mats.
3.2.
SOL INFILTRATION
The DTA/TGA curves of the K342 silica sol used are shown in Figure 6. The
DTA curve shows that there is a small peak at 1400 C which can be attributed
to crystallisation [12]. This crystallisation temperature is much higher than the
intended dwell temperature of 850 C and the deposited silica in the final composite
will therefore still be amorphous after sintering. The TGA curve in Figure 6 shows
that there is less than 1% weight loss in the deposited silica up to temperatures of
1400 C. This sol is therefore ideal for use as the infiltrating medium as there will
216
Figure 7. Graph of the thickness of excess silica deposited on the outer surfaces of woven
fibre mats as a function of deposition time and at different applied deposition voltages.
be negligible weight loss on sintering at 850 C after forming a dense green body
using EPD.
The aim of the EPD stage is to achieve a fully infiltrated preform with the minimum amount of excess material being present in the outer regions of the preform.
Thinner excess silica layers are beneficial because they reduce the propensity for
large drying cracks to form on sintering. These cracks occur due to the differential
shrinkage of the sol network on drying, which generates tensile stresses at the
surface and leads to the initiation and growth of cracks [30]. These tensile stresses
are much lower with thinner sections, and hence the propensity for the initiation
and growth of drying cracks is also reduced. In addition, thinner infiltrated silica
sections allow for the use of more waste glass in the layers in between the silicainfiltrated preforms. The graph in Figure 7 shows the results of the infiltration of
metallic preforms using EPD in terms of the thickness of excess silica deposited on
the outside of the preforms under different applied voltages. When using an applied
voltage of 2 V, the thickness of excess silica did not change significantly with time,
indicating that the applied electric field was too low to influence the movement of
the silica sol particles and cause adequate deposition. Higher voltages of 4 V and
5 V produced deposition thicknesses which appeared linear over the time period
studied.
It was also necessary to avoid significant electrolysis of the water as this led
to gas evolution at the electrodes and subsequent bubble entrapment/pores in the
infiltrated preforms. Each infiltrated preform was examined using SEM and the
best result was achieved using 4 V for 60 s. An example of two infiltrated preforms
is shown in Figure 8. Figure 8(a) shows a preform infiltrated using a voltage of 5 V
217
(a)
(b)
Figure 8. Scanning electron micrograph of EPD-infiltrated woven metal preforms. (a) A preform infiltrated using an applied voltage of 5 V for 480 seconds (note the excessive amount of
silica and the presence of porosity in the deposited layer). (b) A preform infiltrated using an
applied voltage of 4 V for 60 seconds exhibiting a more ideal microstructure.
218
Figure 9. Scanning electron micrograph of a woven metal fibre reinforced waste glass matrix
composite. CTE mismatch-induced cracks can been seen in the central sol-infiltrated region.
These cracks run perpendicular to the dry pressing direction.
for 480 s and it can be seen that, although the fibre region is fully infiltrated, there
is an excessive amount of deposited silica on the outer edges of the preform. The
presence of a large pore produced due to gas bubble entrapment should be noted
also. Figure 8(b) shows a preform infiltrated using EPD parameters of 4 V for 60 s.
The fibre tow regions are fully infiltrated, there is an acceptable level of excess
silica in the outer preform regions, and there are no entrapped gas bubbles. There
are some drying cracks present, however, which will not be eliminated on sintering
due to the low processing temperature employed. In the present system, the consolidation temperature is too low for the densification of the silica via a viscous
flow led mechanism and hence these cracks will not be able to heal on sintering
at 850 C. It has been found by experiment that the sol used in this work requires
temperatures in excess of 1170 C to densify via a viscous flow mechanism [31].
3.3.
COMPOSITE FABRICATION
219
the waste glass matrix with the infiltrated silica region, it has been observed that
during sintering the waste glass shrinks more than the silica due to its higher CTE
in this temperature range. As a result of this differential shrinkage, coupled with
the laminar nature of the composite, tensile stresses are generated parallel to the
dry pressing direction. These stresses are large enough to initiate and propagate
cracks in the weaker, porous, infiltrated silica region, and these cracks can be seen
running perpendicular to the pressing direction in Figure 9. This CTE mismatch
problem would be present to a greater or lesser extent depending on the type of
waste glass used as a matrix material and the type of silica used to infiltrate the
fibres. The problem can be minimised, however, by first obtaining a waste glass,
and then synthesising a silica source that has a CTE which is similar to that of the
matrix, as described below.
It must be stated at this point that no mechanical data were generated for this
composite as it was processed to demonstrate the feasibility of using a waste glass
to fabricate a composite material. Nevertheless, it is envisaged that in mechanical
tests, the porous silica layer in this composite would promote delamination of the
fibre region from the glass matrix region, thus affording some type of debonding on
deformation. In order to promote true composite behaviour, however, the present
silica sol should be used as a fibre coating which would be porous and weak at
850 C and could be applied as a coating to the metal fibres using a recently developed dip-coating technique for 3D woven fibre architectures [32]. The remaining
inter-fibre region would then be infiltrated with a borosilicate sol which densifies
viscously in the 850 C temperature region. This sol would need to be synthesised using sol gel/hydrothermal processing techniques. With these techniques it
is possible to synthesise glasses of many different compositions, and in this way
the physical properties of the final glass could be tailored to match the CTE of
the matrix region, thereby reducing CTE mismatch problems highlighted earlier.
Consolidation of the preform could be improved also by incorporating wet powder
greenbody methods, for example, pressure filtration. This wet greenbody formation
technique has been used successfully with other woven fibre reinforced composite
systems e.g. alumina/alumina [33], mullite/mullite [34] and alumina/mullite [35].
The processing issues involved in recycling a waste glass material in order to
fabricate a woven metal reinforced GMC have been discussed in this work. Ideally,
a composite material of this nature should contain in the region of 40 vol.-% metallic reinforcement in order to exploit fully the toughening capability of this phase.
Although more studies are required in order to fabricate and mechanically test
such a material, the main fibre infiltration/composite fabrication issues which need
to be addressed in order to reach this stage have, however, have been demonstrated
experimentally.
220
4. Conclusions
The recycling of waste glass is a viable option for use in composite materials
from both a cost-effective point of view and also from an environmental aspect.
A processing route has been presented for the fabrication of woven metallic fibre
mat reinforced waste glass matrix composites which involves the use of a silica sol
to infiltrate the intra tow regions of the metallic fibre mats using electrophoretic deposition. The composites were consolidated by uniaxial cold pressing and sintering
of impregnated fibre mats sandwiched between layers of the matrix glass powder.
By pressureless sintering for 1 h at 850 C, composite materials of sufficient integrity could be obtained. The deposited silica provides a porous interface between
the glass matrix and the metallic reinforcement region thus imparting pseudo
composite behaviour to the material. The system needs to be developed further,
however (e.g. a nanosized borosilicate-based sol for the infiltration of preforms,
and the incorporation of a weak fibre/matrix interface), in order to achieve true
composite behaviour, and this matter is the subject of ongoing studies.
Acknowledgements
Professors M. H. Loretto and I. R. Harris are acknowledged for the provision of
laboratory facilities at the IRC in Materials for High Performance Applications and
the School of Metallurgy and Materials, at the University of Birmingham, respectively. The authors would like to acknowledge Andrew Barton for his experimental
assistance. N. V. Bekaert S. A. (Belgium), is acknowledged for supplying the fibre
mats and Degussa Ltd (Germany) are acknowledged for supplying the silica sol.
References
1.
2.
3.
4.
5.
6.
7.
8.
Donald, I. W., Metcalfe, B. L., and Bye, A. D., Preparation of a Novel Unidirectionally Aligned
Microwire-Reinforced Glass Matrix Composite, J. Mat. Sci. Lett. 7, 1988, 964966.
Baran, G., Degrange, M., Roques-Carmes, C., and Wehbi, D., Fracture Toughness of Metal
Reinforced Glass Composite, J. Mat. Sci. 25, 1990, 42114215.
Boccaccini, A. R., Ondracek, G., and Syhre, C., Borosilicate Glass Matrix Composites
Reinforced with Short Metal Fibres, Glastech. Ber. Glass Sci. Technol. 67, 1994, 1620.
Van Landuyt, P., Michel, D., Nicks, L., Streydio, J.-M., Munting, E., and Delannay, F., Processing and Characterisation of a Biocompatible Glass Matrix Composite Reinforced with Titanium
Fibres, Silicates Industrial 910, 1995, 257259.
Dlouhy, I. and Boccaccini, A. R., Preparation, Microstructure and Mechanical Properties of
Metal Particulate Glass-Matrix Composites, Composites Science and Technology 56, 1996,
14151424.
Donald, I. W. and Metcalfe, B. L., The Preparation, Properties and Applications of Some
Glass-Coated Metal Filaments Prepared by the Taylor-Wire Process, J. Mat. Sci. 31, 1996,
11391149.
Ashby, M. F., Blunt, F. J., and Bannister, M., Flow Characteristics of Highly Constrained Metal
Wires, Acta Metall. 37, 1989, 18471857.
Trusty, P. A. and Yeomans, J. A., The Toughening of Alumina with Iron Effects of Iron
Distribution on Fracture Toughness, J. Euro. Ceram. Soc. 17(4), 1997, 495504.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
221
Sigl, L. S. and Fischmeister, H. F., On the Fracture Toughness of Cemented Carbides, Acta
Metall. 36, 1988, 887.
Vaidya, R. U. and Subramanian, K. N., Effect of Ribbon Orientation on the Fracture Toughness
of a Metallic-Glass-Ribbon-Reinforced Glass-Ceramic Matrix Composite, J. Am. Ceram. Soc.
73, 1990, 29622964.
Ducheyne, P. and Hench, L. L., The Processing and Static Mechanical Properties of Metal
Fibre Reinforced Bioglass, J. Mat. Sci. 17, 1982, 595606.
Illston, T. J., Ponton, C. B., Marquis, P. M., and Butler, E. G., The Manufacture of Woven Fibre
Ceramic Matrix Composites Using Electrophoretic Deposition, in P. Duran and J. F. Fernandez
(eds), Third Euroceramics, Vol. 1, Faenza Editrice Iberica, Madrid, 1993, pp. 419424.
Trusty, P. A., Boccaccini, A. R., Butler, E. G., and Ponton, C. B., Novel Techniques for Manufacturing Woven Fiber Reinforced Ceramic Matrix Composites. I. Preform Fabrication, Mat.
and Manuf. Processes 10, 1995, 12151226.
Boccaccini, A. R., Ovenstone, J., and Trusty, P. A., Fabrication of Woven Metal Fibre
Reinforced Glass Matrix Composites, Appl. Comp. Mat. 4, 1997, 145155.
Rutkovskij, A. E., Sarkisov, P. D., Ivashin, A. A., and Budov, V. V., Glass Ceramic-Based
Composites, in V. I. Trefilov (ed.), Ceramic- and Carbon-Matrix Composites, Chapman and
Hall, London, 1994, pp. 255285.
Bekitherm, Heat Resistant Separation Materials, N. V. Bekaert and S. A. Zwevegem, Belgium,
Product Information.
Boccaccini, A. R., Bcker, M., Bossert, J., and Marszalek, K., Glass Matrix Composites from
Coal Flyash and Waste Glass, Waste Management, 1997 (in press).
Jablonski, G. L. and Tyron, S. S., Overview of Coal Combustion By-Product Utilization,
in Proc. 5th Int. Pittsburgh Coal Conference, University of Pittsburgh, Pittsburgh, PA, 1988,
pp. 1521.
Boccaccini, A. R., Kpf, M., and Stumpfe, W., Glass-Ceramics from Filter Dusts from Waste
Incinerators, Ceram. Int. 21, 1995, 231235.
Ponton, C. B., Rawlings, R. D., and Rogers, P. S., Mechanical Properties of Silceram GlassCeramics, Proc. Brit. Ceram. Soc. 37, 1986, 229234.
Lindig, M., Recycling von Fernsehglas, Glastech. Ber. Glass Sci. Technol. 67, 1994, N95
N97.
Greulich, N. and Hnlich, Th., Elution von Bildrhrenglass zur Charakterisierung seines
Deponieverhaltens, Glastech. Ber. Glass Sci. Technol. 69, 1996, N77N81.
Brown, I. W. M. and MacKenzie, K. J. D., Process Design for the Production of a Ceramic-Like
Body from Recycled Waste Glass, J. Mat. Sci. 17, 1982, 21642170.
Clasen, R., Kravtchenko, I., and Ondracek, G., Fibre Preparation from TV Glass for Fibre
Reinforced Recycling Products, in H. Warlimont (ed.), Environmental Aspects in Materials
Research, DGM Oberursel, 1995, pp. 301304.
Boccaccini, A. R., Bcker, M., Trusty, P. A., Romero, M., and Rincn, J. Ma., Sintering Behaviour of Compacts Made from Television Tube (TV) Glasses, Glass Technology 38, 1997,
128133.
Particle Technology Ltd., Borosilicate Glass Batch No. 2210, Derbyshire, UK, Product
Information.
Pernot, F. and Rogier, R., Mechanical Properties of Phosphate Glass-Ceramic-316L StainlessSteel Composites, J. Mat. Sci. 28, 1993, 66766682.
Andrews, J. M., Collins, A. H., Cornish, D. C., and Dracass, J., The Forming of Ceramic
Bodies by Electrophoretic Deposition, Proc. Br. Ceram. Soc. 12, 1969, 211229.
Verwey, J. W. M., Imbusch, G. F., and Blasse, G., Laser Excited Spectroscopy of Gd3+ Ions in
Crystalline and Glass Borate Hosts with Comparable Composition, Phys. Chem. Solids. 50(8),
1989, 813820.
Brinker, C. J. and Scherer, G. W., Sol-Gel Science, Academic Press, New York, 1990.
222
31.
32.
33.
34.
35.