GB2253627A - Alkaline resol phenol-aldehyde resin binder compositions - Google Patents
Alkaline resol phenol-aldehyde resin binder compositions Download PDFInfo
- Publication number
- GB2253627A GB2253627A GB9202497A GB9202497A GB2253627A GB 2253627 A GB2253627 A GB 2253627A GB 9202497 A GB9202497 A GB 9202497A GB 9202497 A GB9202497 A GB 9202497A GB 2253627 A GB2253627 A GB 2253627A
- Authority
- GB
- United Kingdom
- Prior art keywords
- binder composition
- dimethyl ether
- glycol dimethyl
- resin
- binder
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/162—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents use of a gaseous treating agent for hardening the binder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
- B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B22C1/2246—Condensation polymers of aldehydes and ketones
- B22C1/2253—Condensation polymers of aldehydes and ketones with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Mold Materials And Core Materials (AREA)
Abstract
A binder composition for producing articles of bonded particulate material such as foundry moulds or cores comprises an alkaline aqueous solution of a resol phenol-aldehyde resin, an oxyanion which can form a stable complex with the resin, and an ethylene glycol dimethyl ether, and the amount of alkali present in the solution is sufficient to substantially prevent stable complex formation between the resin and the oxyanion. Bonded articles are produced by passing carbon dioxide gas through articles formed from a mixture of particulate material and the binder composition so as to produce stable complex formation and curing of the resin. The ethylene glycol dimethyl ether may be mono-, di, tri- or tetra-ethylene glycol dimethyl ether. A silane, e.g. gamma aminopropyltriethoxysilane, may be present in the binder. The oxyanion may be a borate.
Description
ALKALINE RESOL PHENOL-ALDEHYDE
RESIN BINDER COMPOSITIONS
This invention relates to alkaline resol phenol-aldehyde binder compositions and their use in the production of articles of bonded particulate material such as foundry moulds or cores.
European Patent Application Publication No.
0323096A describes a binder composition comprising an alkaline aqueous solution of a resol phenol-aldehyde resin and an oxyanion which can form a stable complex formation between the resin and the oxyanion. EP 0323096A also describes a process for the production of an article of bonded particulate material, such as a foundry mould or core, in which a mixture of particulate material and the binder composition is formed to a desired shape, and carbon dioxide gas is then passed through the formed shape so as to cause the oxyanion to form a stable complex with the resin and thereby to cure the resin.
It has now been found that the performance of the binder composition can be improved if the binder composition also contains an ethylene glycol dimethyl ether.
According to the present invention there is provided a binder composition comprising an alkaline aqueous solution of a resol phenol-aldehyde resin and an oxyanion which can form a stable complex with the resin, the amount of alkali present in the solution being sufficient to substantially prevent stable complex formation between the resin and the oxyanion, wherein the binder composition also contains an ethylene glycol dimethyl ether.
According to a further feature of the invention there is provided a process for the production of an article of bonded particulate material comprising forming to the desired shape a mixture of particulate material and a binder composition comprising an alkaline aqueous solution of a resol phenol-aldehyde resin, an oxyanion which can form a stable complex with the resin, and an ethylene glycol dimethyl ether, and passing carbon dioxide gas through the formed shape so as to cause the oxyanion to form a stable complex with the resin, and thereby to cure the resin.
The binder composition and the process of the invention are of particular value for making foundry moulds and cores and it is with reference to that application that the invention will be described.
Suitable phenol-aldehyde resins and oxyanions for use in the binder compositions of the invention, and suitable methods for producing the phenol-aldehyde resin are described in EP 0323096A the disclosure of which is incorporated herein by reference.
The ethylene glycol dimethyl ether may be for example monoethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme) or tetraethylene glycol dimethyl ether (tetraglyme). Other alkyl ethers of ethylene glycol other than dimethyl ethers such as monoethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether and ethylene glycol butyl ether ethyl ether are unsuitable as additives to aqueous alkaline phenol-aldehyde resol resin solutions containing an oxyanion such as a borate as on mixing into the solution an emulsion is formed and on standing a layer of liquid separates out.
Diethylene glycol dimethyl ether or triethylene glycol dimethyl ether are preferred.
The optimum amount of ethylene glycol dimethyl ether contained in the binder composition will vary depending on the composition of the resin and on the particular ethylene glycol dimethyl ether used, but will usually be within the range of 1% -10% by weight, preferably 2 - 5%, based on the weight of the binder composition.
The presence of the ethylene glycol dimethyl ether may have one or more beneficial effects on the performance of the binder composition as a binder for making foundry moulds and cores, depending on the composition of the particular resin and the ethylene glycol dimethyl ether used.
The beneficial effects include:
(i) improved mould or core strength
immediately after gassing with carbon
dioxide gas.
(ii) improved strength after gassed moulds or
cores have been stored before use, for
example for up to 24 hours or longer.
(iii) improved strength of moulds or cores
which have been coated with an alcohol
based coating which has been dried by
burning off the alcohol, prior to
storage of the moulds or cores.
(iv) improved mixed sand flowability.
(v) improved mould or core surface finish
and edge hardness.
The binder composition of the invention preferably also contains a silane such as gammaaminopropyltriethoxysilane, N-(2-aminoethyl)-3aminopropyltrimethoxysilane, phenol trimethoxysilane or gammaglycidoxypropyltrimethoxysilane usually in an amount of 0.2% to 1.0% by weight based on the weight of the binder composition.
The following Examples will serve to illustrate the invention:
EXAMPLE 1
A resol phenol-formaldehyde resin was synthesised having the following composition:
phenol 800.00g 91% W/W paraformaldehyde 642.20g
50% W/W sodium hydroxide solution 40.85g
F:P molar ratio 2.3:1
OH :P molar ratio 0.06:1
Water in starting composition 5.2% W/W
The following procedure was used:
1. Charge and melt phenol
2. Charge paraformaldehyde and part of the
sodium hydroxide solution and heat to 60
- 65"C at a rate of 1"C per minute
3. Cool to counteract exothermic reaction
and maintain at 60 - 65 C while adding
the remainder of the sodium hydroxide
solution over a period of 1 hour
4. Heat to 75"C at a rate of 1'C per minute
5.Maintain at 75"C for 30 minutes
6. Heat to 85"C at a rate of 1"C per minute
7. Maintain at 85"C for sufficient time for
the resin to reach a viscosity of 4000
6000 cp at 25"C as measured on a 25g
sample diluted with 15g of 50% w/w
potassium hydroxide solution using Paint
Research Association Bubble Viscosity
Tubes.
The resin was used to produce a base binder (1) having the following composition by weight:
resin 25 parts
50% W/W potassium hydroxide solution 35 parts
borax 5.5 parts
gamma aminopropyltriethoxysilane 0.39 parts
The potassium hydroxide solution was added to the resin, the temperature rise due to exothermic reaction was controlled and the resin was cooled. The borax was added and mixed into the resin until it had dissolved. The silane was then added at a temperature of below 30or.
Binder compositions 2 and 3 were prepared from some of the base binder 1 by dissolving respectively 2% by weight of monoethylene glycol dimethyl ether and 2% by weight of diethylene glycol dimethyl ether in 98% by weight of base binder 1.
All three binders were tested as binders for foundry sand using the following procedure:
3% by weight of the binder based on the weight of sand was mixed with Chelford 60 sand (AFS Fineness
No. 62) and the mixture was used to prepare standard
AFS 50 mm X 50 mm diameter cylindrical cores. The sand temperature was 19 C. The cores were hardened by the passage of carbon dioxide gas for various times at 0.35 kg/cm2 line pressure and a 6.0 litres per minute flow rate.
Some of the cores were tested immediately after gassing on a George Fischer Universal Strength
Machine Type PFA fitted with a High-Dry Compressive
Strength Attachment Type PHD. Some were tested after storage for 3 days in dry storage conditions (temperature 18 - 20 C, relative humidity 40 - 45%) and others were tested after storage for 3 days in humid storage conditions (temperature 24 - 26 C, relative humidity 75 - 80%).
The results obtained are tabulated in Table 1 below.
COMPRESSION STRENGTH (kg/cm2)
BINDER 1 2 3
AS GASSED
GASSING TIME 30S 13.8 16.2 17.3
60S 15.9 16.1 19.6
120S 18.8 18.2 21.1
DRY STORAGE
GASSING TIME 30S 20.7 22.6 27.6
60S 21.3 23.0 33.8
120S 20.5 23.6 28.9
HUMID STORAGE
GASSING TIME 30S 20.3 20.4 26.1
60S 20.3 22.8 30.3
120S 20.3 22.6 28.3
TABLE 1
The results show that diethylene glycol dimethyl ether is a superior additive to monoethylene glycol dimethyl ether in terms of core strengths achieved. Monoethylene glycol dimethyl ether also suffers from the disadvantage that it has an unpleasant smell.
EXAMPLE 2
Using some of the base binder 1 of Example 1 two binder compositions, 4 and 5 were prepared by dissolving respectively 5% by weight of monoethylene glycol dimethyl ether and 5% by weight of diethylene glycol dimethyl ether in 95% by weight of base binder 1.
Binders 1, 4 and 5 were tested as described in
Example 1 under the same conditions as those for the tests of Example 1.
The results obtained are tabulated in Table 2 below.
COMPRESSION STRENGTH (kg/cm2)
BINDER 1 4 5
AS GASSED
GASSING TIME 30S 14.3 14.5 23.0 60s 16.5 15.7 22.0
120S 18.7 17.9 22.5
DRY STORAGE
GASSING TIME 30S 20.2 16.6 33,5 60S 22.2 20.8 32.0
120S 21.1 19.9 32.3
HUMID STORAGE
GASSING TIME 30S 18.8 20.5 28.5
60S 20.7 20.4 28.7
120S 20.5 20.4 28.4
TABLE 2
At the 5% by weight addition level the monoethylene glycol dimethyl ether was inferior compared with the 2% level whereas at the 5% level the di ethylene glycol dimethyl ether gave greater improvements than at the 2% level.
EXAMPLE 3
Using some of the base binder 1 of Example 1 two binder compositions, 6 and 7 were prepared by dissolving respectively 2% by weight of triethylene glycol dimethyl ether and 2% by weight of tetraethylene glycol dimethyl ether in 98% by weight of base binder 1.
Binders 1, 6 and 7 were tested as described in
Example 1 except that the cores were stored for 24 hours. The sand temperature was 19"C, the dry storage conditions were 18 - 20 C and 30 - 35% relative humidity and the humid storage conditions were 24 - 260C and 90 - 95% relative humidity.
The results obtained are tabulated in Table 3 below.
COMPRESSION STRENGTH (kg/cm2)
BINDER 1 6 7
AS GASSED
GASSING TIME 30S 13.1 14.0 14.3
60S 14.7 17.4 17.0
120s 17.5 19.2 19.4
DRY STORAGE
GASSING TIME 30S 21.0 30.0 27.8
60S 21.3 29.0 31.0
120S 20.6 29.7 31.6
HUMID STORAGE
GASSING TIME 30S 15.7 19.1 19.5
60S 15.9 21.0 20.2
120S 16.8 19.4 20.2
TABLE 3
Triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether gave similar results and both gave significant improvements in terms of the strength of cores stored under ambient conditions.
EXAMPLE 4
Example 3 was repeated using binders 8 and 9, which contained respectively 5% by weight triethylene glycol dimethyl ether and 5% by weight of tetraethylene glycol dimethyl ether, instead of binders 6 and 7. The cores were stored for 4 days instead of 24 hours.
The results obtained are tabulated in Table 4 below.
COMPRESSION STRENGTH (kg/cm2)
BINDER 1 8 9
AS GASSED
GASSING TIME 30S 13.3 15.8 15.4
60S 15.4 18.0 17.8
120S 18.0 19.7 20.6
DRY STORAGE
GASSING TIME 30S 16.8 40.0 NO DATA
60S 21.7 42.0 41.0
120S 24.1 45.0 44.5
HUMID STORAGE
GASSING TIME 30S 15.8 26.1 24.9
60S 16.4 26.5 24.2
120S 16.0 27.1 27.2
TABLE 4
As in Example 3 the two additives both gave similar results, and in terms of the strength of cores stored under dry conditions the improvements obtained were even greater than at the 2% by weight addition level.
EXAMPLE 5
Using the base resin of Example 1 a series of binders 10 - 13, was prepared containing 2%, 4%, 7.5% and 10% by weight respectively of diethylene glycol dimethyl ether based on the weight of the binder.
Binders 10 - 12 were tested using the procedure of Example 1 except that the cores were stored for 24 hours. The sand temperature was 18 18.5"C, the dry storage conditions were 18 - 20"C and 40 - 45% relative humidity, and the humid storage conditions were 25 - 270C and 80 - 95% relative humidity. Binder 13 was not tested because the binder was unstable and diethylene glycol dimethyl ether separated out.
The results obtained are tabulated in Table 5 below.
COMPRESSION STRENGTH (kg/cm2)
BINDER 10 11 12
AS GASSED
GASSING TIME 305 14.9 16.1 15.0
60S 17.0 19.1 16.3
120S 18.6 22.3 17.6
DRY STORAGE
GASSING TIME 30S 30.0 37.0 35.0
60S 29.4 35.5 33.5
120S 31.1 38.0 37.0
HUMID STORAGE
GASSING TIME 30S 19.0 23.9 24.6
60S 21.6 24.8 24.3
120S 22.6 24.6 25.2
TABLE 5
For optimum as-gassed strength the results indicate that the addition level of the diethylene glycol dimethyl ether should be approximately 4% by weight. At higher levels of addition the improvements in the strength of stored cores are still maintained but as-gassed strengths tend to deteriorate.
Claims (10)
1. A binder composition comprising an alkaline aqueous solution of a resol phenol-aldehyde resin and an oxyanion which can form a stable complex with the resin, wherein the amount of alkali present in the solution is sufficient to substantially prevent stable complex formation between the resin and the oxyanion, characterised in that the binder composition also contains an ethylene glycol dimethyl ether.
2. A binder composition according to Claim 1 characterised in that the ethylene glycol dimethyl ether is monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether or tetraethylene glycol dimethyl ether.
3. A binder composition according to Claim 1 or
Claim 2 characterised in that the ethylene glycol dimethyl ether is present in an amount of 1% to 10% by weight based on the weight of the binder composition.
4. A binder composition according to Claim 3 characterised in that the ethylene glycol dimethyl ether is present in an amount of 2% to 5% by weight based on the weight of the binder composition.
5. A binder composition according to any one of
Claims 1 to 4 characterised in that the composition contains in addition a silane.
6. A binder composition according to Claim 5 characterised in that the silane is gammaaminopropyltriethoxysilane, N-(2-aminoethyl)-3aminopropyltrimethoxysilane, phenol trimethoxysilane or gammaglycidoxypropyltrimethoxysilane.
7. A binder composition according to Claim 5 characterised in that the amount of silane present is from 0.25% to 1.0% by weight based on the weight of the binder composition.
8. A binder composition as claimed in Claim 1 substantially as herein described with reference to the
Examples.
9. A process for the production of an article of bonded particulate material in which a mixture comprising particulate material and a binder composition is formed to a desired shape and the binder composition is cured by passing carbon dioxide gas through the formed shape, characterised in that the binder composition used is a composition according to any one of Claims 1 to 7.
10. A process for the production of an article of bonded particulate material as claimed in Claim 9 substantially as herein described with reference to the
Examples.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB919105313A GB9105313D0 (en) | 1991-03-13 | 1991-03-13 | Binder compositions |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9202497D0 GB9202497D0 (en) | 1992-03-25 |
| GB2253627A true GB2253627A (en) | 1992-09-16 |
| GB2253627B GB2253627B (en) | 1994-06-01 |
Family
ID=10691500
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB919105313A Pending GB9105313D0 (en) | 1991-03-13 | 1991-03-13 | Binder compositions |
| GB9202497A Expired - Fee Related GB2253627B (en) | 1991-03-13 | 1992-02-06 | Alkaline resol phenol-aldehyde resin binder compositions |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB919105313A Pending GB9105313D0 (en) | 1991-03-13 | 1991-03-13 | Binder compositions |
Country Status (1)
| Country | Link |
|---|---|
| GB (2) | GB9105313D0 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001012709A1 (en) * | 1999-08-12 | 2001-02-22 | Ashland-Südchemie-Kernfest GmbH | Resol based binding agent containing aluminium and boron |
| DE102016211971A1 (en) | 2016-06-30 | 2018-01-04 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Aqueous alkaline binder composition for curing with carbon dioxide gas and their use, a corresponding molding material mixture for producing a foundry molding, a corresponding foundry molding and a process for producing a foundry molding |
| WO2018002121A1 (en) | 2016-06-30 | 2018-01-04 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Aqueous alkaline binder composition for curing with carbon dioxide gas and use thereof, a corresponding moulding mixture for producing foundry shape, a corresponding foundry shape and a method for producing a foundry shape |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0323096A2 (en) * | 1987-12-24 | 1989-07-05 | Foseco International Limited | Production of articles of bonded particulate material and binder compostions for use therein |
-
1991
- 1991-03-13 GB GB919105313A patent/GB9105313D0/en active Pending
-
1992
- 1992-02-06 GB GB9202497A patent/GB2253627B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0323096A2 (en) * | 1987-12-24 | 1989-07-05 | Foseco International Limited | Production of articles of bonded particulate material and binder compostions for use therein |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001012709A1 (en) * | 1999-08-12 | 2001-02-22 | Ashland-Südchemie-Kernfest GmbH | Resol based binding agent containing aluminium and boron |
| DE102016211971A1 (en) | 2016-06-30 | 2018-01-04 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Aqueous alkaline binder composition for curing with carbon dioxide gas and their use, a corresponding molding material mixture for producing a foundry molding, a corresponding foundry molding and a process for producing a foundry molding |
| WO2018002121A1 (en) | 2016-06-30 | 2018-01-04 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Aqueous alkaline binder composition for curing with carbon dioxide gas and use thereof, a corresponding moulding mixture for producing foundry shape, a corresponding foundry shape and a method for producing a foundry shape |
| WO2018002129A1 (en) | 2016-06-30 | 2018-01-04 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Aqueous akaline binder composition for curing with carbon dioxide gas and use thereof, a corresponding moulding mixture for a producing foundry shape, a corresponding foundry shape and a method for producing a foundry shape |
| DE102016211970A1 (en) | 2016-06-30 | 2018-01-18 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Aqueous alkaline binder composition for curing with carbon dioxide gas and their use, a corresponding molding material mixture for producing a foundry molding, a corresponding foundry molding and a process for producing a foundry molding |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2253627B (en) | 1994-06-01 |
| GB9202497D0 (en) | 1992-03-25 |
| GB9105313D0 (en) | 1991-04-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19970206 |