EP0986442B1 - Method and apparatus for supplying an optimised quantity of catalyst to a core shooting machine - Google Patents
Method and apparatus for supplying an optimised quantity of catalyst to a core shooting machine Download PDFInfo
- Publication number
- EP0986442B1 EP0986442B1 EP98922962A EP98922962A EP0986442B1 EP 0986442 B1 EP0986442 B1 EP 0986442B1 EP 98922962 A EP98922962 A EP 98922962A EP 98922962 A EP98922962 A EP 98922962A EP 0986442 B1 EP0986442 B1 EP 0986442B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- shooting machine
- pressure container
- core shooting
- purging gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/12—Treating moulds or cores, e.g. drying, hardening
- B22C9/123—Gas-hardening
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/12—Treating moulds or cores, e.g. drying, hardening
Definitions
- This invention relates to a method and apparatus for the supply of an optimised quantity of catalyst to a core shooting machine for the manufacture of cores and moulds for casting processes wherein the catalyst is extracted from a pressurised vessel in liquid or gaseous form and is mixed with a purging gas before it is introduced into the core shooting machine.
- the document DE-A-2413537 teaches a method and an apparatus for the supply of a catalyst to a core shooting machine according to the preamble of claim 1 and 6 respectively.
- TMA trimethylamine
- a method for the manufacture of cores for casting processes is described in DE 19706472.8 in which gaseous trimethylamine is conducted through parts of a metering device and then, in a concentration of from 0.01 to 0.12 wt-% based on the quantity of sand used per core, it is conducted into the core shooting machine, and is there brought into contact with the sand.
- the gaseous trimethylamine is exposed to a purging gas.
- a connector is located in the conduit for the purging gas which in this manner is brought into contact with the catalyst.
- the object of the invention therefore is to provide a method and apparatus for adding an optimised quantity of catalyst to a core shooting machine for the production of cores or moulds for casting processes in which it is ensured that the core shooting machine is exposed to the optimised quantity of catalyst in the shortest possible time.
- a method for the supply of an optimised quantity of catalyst to a core shooting machine for the manufacture of cores or moulds for casting processes wherein a catalyst is extracted from a pressurised vessel (1) in liquid or gaseous form and is mixed with a purging gas before it is introduced into the core shooting machine, characterised in that firstly an optimised quantity of catalyst and secondly the purging gas at a pressure of 0.1 to 10 bar are fed into a pressure container (15), the pressure container is then closed so that the catalyst and purging gas are mixed in the pressure container (15), and the resulting mixture is introduced into the core shooting machine.
- core shooting machine shall be understood to include devices or apparatus used in foundries for the manufacture of moulds for casting processes.
- the catalyst may be for example a tertiary amine (such as trimethylamine), methyl formate, sulphur dioxide or carbon dioxide.
- the method is particularly useful for producing cores or moulds using a benzyl ether resin and an isocyanate and a tertiary amine such as triethylamine as catalyst.
- a gas bottle may be used for example as the pressurised vessel containing the catalyst.
- air is used as the purging gas but other gases, for example carbon dioxide, may be used.
- the supply of purging gas to the pressure container at 0.1 to 10 bar makes it possible to adjust the pressure in the pressure container within the range from 0.1 to 10 bar.
- the catalyst supply takes place through a valve.
- the optimised quantity of catalyst depends on the size of the core or mould being produced, and is determined in advance on the basis of various parameters for a particular core or mould.
- the catalyst in gaseous form is heated in the pressurised vessel to 3 to 80 °C to facilitate contact between the catalyst and the purging gas.
- the catalyst is conducted to metering bellows in liquid form before being fed in gaseous form to the pressure container.
- the use of the metering bellows is advantageous because although heat is extracted from the surroundings during the transformation of the catalyst from the liquid to the gaseous form the metering bellows remain able to continue to function over extended periods of operation when compared with other conveying equipment. It is particularly advantageous that the metering bellows can be installed in a relatively simple manner because older core or mould production plants can be adapted to use this embodiment of the method of the invention.
- trimethylamine is used as the catalyst, and it is advantageous that when using trimethylamine the quantity of catalyst can be kept relatively small because the nuisance from odour when cores are subsequently stored before use can largely be avoided.
- apparatus for the supply of an optimised quantity of catalyst to a core shooting machine for the manufacture of cores or mould for casting processes comprising a pressurised vessel for containing the catalyst, means for conducting the catalyst to a conduit for supplying the catalyst to a core shooting machine, and means for supplying a purging gas to the apparatus, characterised by means for determining the quantity of catalyst in the pressurised vessel, and in that the apparatus also has a pressure container located between and connected to the pressurised vessel and the supply conduit, and the purging gas supply means is connected to the pressure container, the apparatus further comprising valves to close the pressure container, so that an optimised mixture of catalyst and purging gas present in the pressure container may be introduced into the core shooting machine.
- the apparatus may also have a heater for heating the catalyst in the pressurised vessel.
- Such apparatus is suitable for use when the catalyst in the pressurised vessel is in gaseous form.
- the apparatus may have metering bellows located between the pressurised vessel and the pressure container so that the catalyst may be transformed into the gaseous form before being fed into the pressure container.
- a catalyst is contained in a pressurised vessel (1), which may be a simple gas bottle, and the pressurised vessel (1) is located on scales (2) in order to determine its contents.
- the pressurised vessel (1) can be heated by means of heater (3).
- the catalyst is conducted through a valve (4) into supply conduit (5) which leads directly to the a core shooting machine (not shown).
- a purging gas is introduced directly into the supply conduit (5) through conduit (6).
- the quantity of catalyst which reaches supply conduit (5) is reduced.
- the pressure selected in the conduit (6) for the purging gas cannot be too great.
- the pressure which exists in the supply conduit (5) is therefore insufficient to conduct the quantity of catalyst through the core shooting machine in as short a time as is desirable.
- a catalyst is contained in a pressurised vessel (11), which may be a simple gas bottle, and the pressurised vessel (11) is located on scales (12) in order to determine its contents.
- the pressurised vessel (11) can be heated by means of heater (13).
- a previously determined optimum quantity of catalyst is introduced via first valve (14) into pressure container (15) and first valve (14) is closed.
- Purging gas is supplied to the pressure container (15) through conduit (16) via second valve (17) at a pressure of 0.1 to 10 bar.
- Second valve (17) is then closed and third valve (18) is opened so as to introduce the mixture of catalyst and purging gas which is present in the pressure container (15) into supply conduit (19) and into the core shooting machine (not shown).
- Figure 3 shows similar apparatus to that shown in Figure 2 but the apparatus also has metering bellows (20) an additional fourth valve (21) located between first valve (14) and pressure container (15) and there is no heater.
- liquid catalyst in the pressurised vessel (11) is conducted through first valve (14) into the metering bellows (20) where the catalyst is transformed from the liquid to the gaseous state.
- First valve (14) is then closed and fourth valve (21) is opened, and the gaseous optimised quantity of catalyst is introduced into the pressure container (15), while the second valve (17) and the third valve (18) remain closed.
- the fourth valve (21) has been closed the second valve (17) is opened and purging air is introduced into pressure container (15).
- the third valve (18) is then opened and the mixture of catalyst and purging gas is introduced to a core shooting machine (not shown) via supply conduit (19).
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Molds, Cores, And Manufacturing Methods Thereof (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Description
This invention relates to a method and apparatus for the supply of an
optimised quantity of catalyst to a core shooting machine for the manufacture of
cores and moulds for casting processes wherein the catalyst is extracted from a
pressurised vessel in liquid or gaseous form and is mixed with a purging gas
before it is introduced into the core shooting machine.
The document DE-A-2413537 teaches a method and an
apparatus for the supply of a catalyst to a core shooting
machine according to the preamble of claim 1 and 6 respectively.
Methods are known for the manufacture of cores for casting
processes. The application of amines as catalysts for the manufacture of cores
according to the urethane Cold Box Process is described in the special issue of
Giesserei 78 (1991), volume 11, pages 372 to 374. In this known method for core
and mould production a moulding material is used containing a benzyl ether resin
(ortho-phenol resol) and an isocyanate which is cured with a tertiary amine
catalyst. As the catalytic effect of the amine is particularly advantageous in the
gaseous phase, tests were carried out using trimethylamine (TMA) whose boiling
point is about 3 °C, and with which, for this reason, curing is possible in a
relatively simple manner with a gaseous amine. The accelerating effect of a
tertiary amine by the formation of reactive transitional compounds during the
polyurethane reaction is described by the following reaction equation :
When making cores by this known method it is disadvantageous that
the tertiary amine is fed to the core shooting machine considerably in excess of
the required amount. Although it has been shown that the application of
trimethylamine makes it possible to advantageously reduce the amount of amine
used by about 50% in comparison to other amines, the application of
trimethylamine still has associated disadvantages. One problem is the extreme
nuisance created by the odour which makes it essential that all parts of the
equipment used are absolutely leak proof. All pipework must there be insulated
at relatively high expense.
A method for the manufacture of cores for casting processes is
described in DE 19706472.8 in which gaseous trimethylamine is conducted
through parts of a metering device and then, in a concentration of from 0.01 to
0.12 wt-% based on the quantity of sand used per core, it is conducted into the
core shooting machine, and is there brought into contact with the sand.
According to a preferred embodiment of this method it is envisaged that the
gaseous trimethylamine is exposed to a purging gas. In general according to the
method described in DE 19706472.8 it is envisaged to take the trimethylamine
from a pressurised vessel and conduct it to the core shooting machine by means
of a conduit. A connector is located in the conduit for the purging gas which in
this manner is brought into contact with the catalyst. However it is
disadvantageous when using this method that the quantity of catalyst which is
conducted to the core shooting machine decreases as a result of a decrease of
the pressure in the pressurised vessel. Therefore the addition of and/or the
setting for an optimised quantity of catalyst is not possible. Furthermore, it is
disadvantageous that the pressure at which the mixture of catalyst and purging
gas is conducted to the core shooting machine is relatively low, as it is not
possible to conduct the mixture of catalyst and purging gas through the core
shooting machine at the desired speed.
The object of the invention therefore is to provide a method and
apparatus for adding an optimised quantity of catalyst to a core shooting machine for
the production of cores or moulds for casting processes in which it is ensured that the
core shooting machine is exposed to the optimised quantity of catalyst in the shortest
possible time.
According to the invention there is provided a method for the supply of an
optimised quantity of catalyst to a core shooting machine for the manufacture of cores
or moulds for casting processes wherein a catalyst is extracted from a pressurised
vessel (1) in liquid or gaseous form and is mixed with a purging gas before it is
introduced into the core shooting machine, characterised in that firstly an optimised
quantity of catalyst and secondly the purging gas at a pressure of 0.1 to 10 bar are fed
into a pressure container (15), the pressure container is then closed so that the catalyst
and purging gas are mixed in the pressure container (15), and the resulting mixture is
introduced into the core shooting machine.
As used herein the term "core shooting machine" shall be understood to
include devices or apparatus used in foundries for the manufacture of moulds for
casting processes.
The catalyst may be for example a tertiary amine (such as
trimethylamine), methyl formate, sulphur dioxide or carbon dioxide. The method is
particularly useful for producing cores or moulds using a benzyl ether resin and an
isocyanate and a tertiary amine such as triethylamine as catalyst.
A gas bottle may be used for example as the pressurised vessel
containing the catalyst. Usually air is used as the purging gas but other gases, for
example carbon dioxide, may be used. The supply of purging gas to the pressure
container at 0.1 to 10 bar makes it possible to adjust the pressure in the pressure
container within the range from 0.1 to 10 bar. Advantageously the catalyst supply takes
place through a valve. The optimised quantity of catalyst
depends on the size of the core or mould being produced, and is determined in
advance on the basis of various parameters for a particular core or mould.
Surprisingly it has been shown that in the process of supplying an
optimised quantity of catalyst to a core shooting machine according to the
invention it is possible in advantageous manner to conduct the optimised quantity
of catalyst through the core shooting machine in an optimised time. The
relationship between the quantity of catalyst on the one hand, and the quantity
of purging gas on the other hand, which is adjusted to between 1 : 1000 and 1 :
10000 can be held constant while the mixture of the two is flowing through the
core shooting machine. In this manner disadvantageous variations in pressure
may be avoided. The optimised time is the shortest time which is necessary for
the mixture to flow completely through the core shooting machine, and it is
regulated by means of the pressure in the pressure container.
In a preferred embodiment of the method of the invention the catalyst
in gaseous form is heated in the pressurised vessel to 3 to 80 °C to facilitate
contact between the catalyst and the purging gas.
According to another preferred embodiment of the method of the
invention the catalyst is conducted to metering bellows in liquid form before being
fed in gaseous form to the pressure container. The use of the metering bellows is
advantageous because although heat is extracted from the surroundings during
the transformation of the catalyst from the liquid to the gaseous form the
metering bellows remain able to continue to function over extended periods of
operation when compared with other conveying equipment. It is particularly
advantageous that the metering bellows can be installed in a relatively simple
manner because older core or mould production plants can be adapted to use
this embodiment of the method of the invention.
According to a further preferred embodiment of the method of the
invention trimethylamine is used as the catalyst, and it is advantageous that when
using trimethylamine the quantity of catalyst can be kept relatively small because the
nuisance from odour when cores are subsequently stored before use can largely be
avoided.
According to a further preferred embodiment of the method of the
invention, after the mixture of catalyst and purging gas have been introduced from the
pressure container into the core shooting machine additional purging gas is fed into the
core shooting machine via the pressure container. This measure has the additional
advantage that it results in purging of the core shooting machine, and the core or
mould and appreciably reduces any nuisance due to the odour from the catalyst
According to a further feature of the invention there is provided apparatus
for the supply of an optimised quantity of catalyst to a core shooting machine for the
manufacture of cores or mould for casting processes comprising a pressurised vessel
for containing the catalyst, means for conducting the catalyst to a conduit for
supplying the catalyst to a core shooting machine, and means for supplying a
purging gas to the apparatus, characterised by means for determining the quantity of catalyst in
the pressurised vessel, and in that the apparatus also has a pressure
container located between and connected to the pressurised vessel and the
supply conduit, and the purging gas supply means is connected to the
pressure container, the apparatus further comprising valves to close the pressure
container, so that an optimised mixture of catalyst and purging gas present in the
pressure container may be introduced into the core shooting machine.
If desired the apparatus may also have a heater for heating the catalyst in
the pressurised vessel.
Such apparatus is suitable for use when the catalyst in the pressurised
vessel is in gaseous form. When the catalyst in the pressurised vessel is in liquid
form the apparatus may have metering bellows located between the pressurised
vessel and the pressure container so that the catalyst may be transformed into
the gaseous form before being fed into the pressure container.
The invention is illustrated in the accompanying drawings in which :-
Referring to Figure 1, a catalyst is contained in a pressurised vessel
(1), which may be a simple gas bottle, and the pressurised vessel (1) is located
on scales (2) in order to determine its contents. The pressurised vessel (1) can
be heated by means of heater (3). In the production of a core or mould the
catalyst is conducted through a valve (4) into supply conduit (5) which leads
directly to the a core shooting machine (not shown). A purging gas is introduced
directly into the supply conduit (5) through conduit (6). With decreasing pressure
in the pressurised vessel (1) the quantity of catalyst which reaches supply
conduit (5) is reduced. Furthermore, in order to prevent the purging gas from
being introduced into the pressurised vessel (1) through the open valve (4) the
pressure selected in the conduit (6) for the purging gas cannot be too great. The
pressure which exists in the supply conduit (5) is therefore insufficient to conduct
the quantity of catalyst through the core shooting machine in as short a time as is
desirable.
Referring to Figure 2, a catalyst is contained in a pressurised
vessel (11), which may be a simple gas bottle, and the pressurised vessel (11) is
located on scales (12) in order to determine its contents. The pressurised vessel (11)
can be heated by means of heater (13). A previously determined optimum quantity of
catalyst is introduced via first valve (14) into pressure container (15) and first valve (14)
is closed. Purging gas is supplied to the pressure container (15) through conduit (16)
via second valve (17) at a pressure of 0.1 to 10 bar. Second valve (17) is then closed
and third valve (18) is opened so as to introduce the mixture of catalyst and purging
gas which is present in the pressure container (15) into supply conduit (19) and into the
core shooting machine (not shown).
Figure 3 shows similar apparatus to that shown in Figure 2 but the
apparatus also has metering bellows (20) an additional fourth valve (21) located
between first valve (14) and pressure container (15) and there is no heater. When the
apparatus is used liquid catalyst in the pressurised vessel (11) is conducted through
first valve (14) into the metering bellows (20) where the catalyst is transformed from the
liquid to the gaseous state. First valve (14) is then closed and fourth valve (21) is
opened, and the gaseous optimised quantity of catalyst is introduced into the pressure
container (15), while the second valve (17) and the third valve (18) remain closed. After
the fourth valve (21) has been closed the second valve (17) is opened and purging air
is introduced into pressure container (15). The third valve (18) is then opened and the
mixture of catalyst and purging gas is introduced to a core shooting machine (not
shown) via supply conduit (19).
Claims (8)
- A method for the supply of an optimised quantity of catalyst to a core shooting machine for the manufacture of cores or moulds for casting processes wherein a catalyst is extracted from a pressurised vessel (11) in liquid or gaseous form and is mixed with a purging gas before it is introduced into the core shooting machine, characterised in that firstly an optimised quantity of catalyst and secondly the purging gas at a pressure of 0.1 to 10 bar are fed into a pressure container (15) the pressure container (15) is then closed so that the catalyst and purging gas are mixed in the pressure container (15), and the resulting mixture is introduced into the core shooting machine.
- A method according to Claim 1 characterised in that the catalyst in gaseous form is heated to 3 to 80 °C in the pressurised vessel (11).
- A method according to Claim 1 characterised in that the catalyst in liquid form is conducted to metering bellows (20) before being fed in gaseous form to the pressure container (15).
- A method according to any one of Claims 1 to 3 characterised in that the catalyst is trimethylamine.
- A method according to any one of Claims 1 to 4 characterised in that after the introduction of the mixture of catalyst and purging gas into the core shooting machine additional purging gas is fed into the core shooting machine through pressure container (15).
- Apparatus for the supply of an optimised quantity of catalyst to a core shooting machine for the manufacture of cores or mould for casting processes comprising a pressurised vessel (11) for containing the catalyst, means (14) for conducting the catalyst to a conduit (19) for supplying the catalyst to a core shooting machine, and means (16, 17) for supplying a purging gas to the apparatus, characterised by means (12) for determining the quantity of catalyst in the pressurised vessel, and in that the apparatus also has a pressure container (15) located between and connected to the pressurised vessel (11) and the supply conduit (19), and the purging gas supply means (16) is connected to the pressure container (15), the apparatus further comprising valves (14,17,18) to close the pressure container (15) so that an optimised mixture of catalyst and purging gas present in the pressure container (15) may be introduced into the core shooting machine
- Apparatus according to Claim 6 characterised in that the apparatus has means (13) for heating the catalyst in the pressurised vessel (11).
- Apparatus according to Claim 6 characterised in that the apparatus has metering, bellows (20) located between the pressurised vessel (11) and the pressure container (15) so that the catalyst may be transformed into the gaseous form before being fed into the pressure container (15).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19723314A DE19723314C1 (en) | 1997-06-04 | 1997-06-04 | Process for supplying an optimized amount of catalyst to a core shooter |
| DE19723314 | 1997-06-04 | ||
| PCT/GB1998/001509 WO1998055249A1 (en) | 1997-06-04 | 1998-05-22 | Method and apparatus for supplying an optimised quantity of catalyst to a core shooting machine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0986442A1 EP0986442A1 (en) | 2000-03-22 |
| EP0986442B1 true EP0986442B1 (en) | 2003-03-19 |
Family
ID=7831310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP98922962A Expired - Lifetime EP0986442B1 (en) | 1997-06-04 | 1998-05-22 | Method and apparatus for supplying an optimised quantity of catalyst to a core shooting machine |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0986442B1 (en) |
| JP (1) | JP2002502317A (en) |
| KR (1) | KR20010013424A (en) |
| CN (1) | CN1265614A (en) |
| AR (1) | AR015384A1 (en) |
| AT (1) | ATE234698T1 (en) |
| AU (1) | AU741268B2 (en) |
| BR (1) | BR9809723A (en) |
| CA (1) | CA2293507A1 (en) |
| DE (2) | DE19723314C1 (en) |
| TR (1) | TR199902962T2 (en) |
| TW (1) | TW396075B (en) |
| WO (1) | WO1998055249A1 (en) |
| ZA (1) | ZA984468B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2734320B1 (en) * | 2011-07-19 | 2016-11-16 | Ask Chemicals L. P. | Method for curing cold-box foundry shape with gaseous catalyst |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2413537C2 (en) * | 1974-03-21 | 1984-11-15 | Horst-Werner Ing.(Grad.) 7707 Engen Michel | Device for manufacturing cores for foundry purposes |
| US4362204A (en) * | 1980-03-17 | 1982-12-07 | The Mead Corporation | Method and apparatus for curing a foundry core |
| JPS59153543A (en) * | 1983-02-22 | 1984-09-01 | Chuzo Gijutsu Fukiyuu Kyokai | Process for supplying hardening gas in gas hardening mold |
| JPS60132639A (en) * | 1983-06-01 | 1985-07-15 | Naniwa Seisakusho:Kk | Gas generating apparatus for molding cold box casting mold |
-
1997
- 1997-06-04 DE DE19723314A patent/DE19723314C1/en not_active Expired - Fee Related
-
1998
- 1998-05-22 DE DE69812354T patent/DE69812354D1/en not_active Expired - Lifetime
- 1998-05-22 BR BR9809723-7A patent/BR9809723A/en unknown
- 1998-05-22 CA CA002293507A patent/CA2293507A1/en not_active Abandoned
- 1998-05-22 AT AT98922962T patent/ATE234698T1/en not_active IP Right Cessation
- 1998-05-22 CN CN98807815A patent/CN1265614A/en active Pending
- 1998-05-22 TR TR1999/02962T patent/TR199902962T2/en unknown
- 1998-05-22 WO PCT/GB1998/001509 patent/WO1998055249A1/en not_active Application Discontinuation
- 1998-05-22 AU AU75421/98A patent/AU741268B2/en not_active Ceased
- 1998-05-22 JP JP50181899A patent/JP2002502317A/en active Pending
- 1998-05-22 EP EP98922962A patent/EP0986442B1/en not_active Expired - Lifetime
- 1998-05-22 KR KR19997011425A patent/KR20010013424A/en not_active Application Discontinuation
- 1998-05-26 ZA ZA984468A patent/ZA984468B/en unknown
- 1998-05-29 TW TW087108368A patent/TW396075B/en not_active IP Right Cessation
- 1998-06-04 AR ARP980102616A patent/AR015384A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ATE234698T1 (en) | 2003-04-15 |
| JP2002502317A (en) | 2002-01-22 |
| BR9809723A (en) | 2000-07-11 |
| AR015384A1 (en) | 2001-05-02 |
| CA2293507A1 (en) | 1998-12-10 |
| AU7542198A (en) | 1998-12-21 |
| WO1998055249A1 (en) | 1998-12-10 |
| AU741268B2 (en) | 2001-11-29 |
| DE69812354D1 (en) | 2003-04-24 |
| CN1265614A (en) | 2000-09-06 |
| TW396075B (en) | 2000-07-01 |
| TR199902962T2 (en) | 2000-05-22 |
| DE19723314C1 (en) | 1999-02-18 |
| ZA984468B (en) | 1998-12-01 |
| KR20010013424A (en) | 2001-02-26 |
| EP0986442A1 (en) | 2000-03-22 |
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