GB2045777A - A silicate, hardener and sugar- based composition and the application thereof in the cold-hardening of sands - Google Patents
A silicate, hardener and sugar- based composition and the application thereof in the cold-hardening of sands Download PDFInfo
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- GB2045777A GB2045777A GB8007656A GB8007656A GB2045777A GB 2045777 A GB2045777 A GB 2045777A GB 8007656 A GB8007656 A GB 8007656A GB 8007656 A GB8007656 A GB 8007656A GB 2045777 A GB2045777 A GB 2045777A
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- composition
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Classifications
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- 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
- B22C1/167—Mixtures of inorganic and organic binding agents
-
- 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
- B22C1/18—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 inorganic agents
- B22C1/186—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 inorganic agents contaming ammonium or metal silicates, silica sols
- B22C1/188—Alkali metal silicates
-
- 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
- B22C1/26—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 carbohydrates; of distillation residues therefrom
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- Mold Materials And Core Materials (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Foundary sand is cold-hardened by means of a composition comprising an aqueous solution of a silicate, a hardener and a sugar, wherein the sugar is a saccharose. This composition is characterized in that the silicate may be an alkaline metal (Me) silicate whose SiO2/Me2O weight ratio is, when Me represents sodium, potassium and lithium, respectively between 1.9 and 2.4; 1.2 and 1.6; 3.9 and 5. The invention applies to the use of regenerated sands for manufacturing moulds and cores.
Description
SPECIFICATION
A silicate, hardener and sugar-based composition and the application thereof in the cold-hardening of sands
The present invention relates to a composition for foundry sands used in the manufacture of moulds and cores, formed from an aqueous solution of a silicate, a hardener and a sugar.
It also relates to a process for cold-hardening foundry sands by means of the composition and particularly foundry sands after their regeneration.
Numerous compositions are known in which alkaline metal silicates are used as binder and there exist a large number of hardeners for these binders.
It is also known that it is possible to use different additives in combination with the binder and hardner, and in particular additives allowing easier stripping the foundry mould.
By way of additives for improving stripping, starches, dextrins, synthetic resins and sugars can be mentioned. However, these additives and especially the sugar additives used up to present for adding to the binder-hardener mixture, adversely influence the life and setting times of the sands.
As for the known compositions based on an alkaline metal silicate and a hardener such as an ester, they often have the major disadvantage of only allowing production of the outer parts of the foundry pieces, i.e.
production of the moulds. In fact, sands hardened by such compositions present after casting and cooling of the metal too high a resistance for considering the manufacture of the inner parts of the foundry pieces or cores.
Furthermore it is known that "burnt" sands, i.e. sands already having served for the manufacture of moulds or cores, are usually regenerated. This regeneration may be carried out in accordance with different processes, among which the hot process adapted to "Croning" sands, and the dry process adapted to furanic, phenolic and siliceous sands which consists in the mechanical separation of the binder sheath agglomerated by the residues surrounding the grains of sand. However as industrial experience and publications show, it is difficult to accept up to present more than 70pro of regenerated sand, previously treated with mineral binders, for forming sands to serve in the manufacture of moulds or cores.A higher proportion of regenerated sand adversely affects the mechanical characteristics, the lifetime and the setting time of the foundry sands.
Now, with a concern for protecting the environment, it would be desirable to limit the discharge of "burnt" sands.
The aim of the invention is to remedy the above-described disadvantages and for this it proposes a composition for foundry sands formed from an aqueous solution of a silicate, a hardener and a sugar, characterized in that the silicate is an alkaline metal silicate whose SiO2/Me2O weight ratio is, when Me represents sodium, potassium and lithium, respectively between 1.9 and 2.4; 1.25 and 1.58; 3,95 and 4.97, and in that the sugar is a saccharose having a purity greater than 99.9%.
The choice of a silicate having a particular weight ratio of modulus is important. A silicate with too high a modulus is not suitable for it confers on the mixture, obtained by adding the composition of the invention to the sand, too short a lifetime; setting, due to the presence of the hardener, begins therefore with the mixing.
For example, a sodium silicate will have to have a modulus lower than 2.4 and greater than 1.9.
It will be noted that in the composition of the invention an organic silicate may also be used, obtained by reaction of silicic acid and an organic base. the modulus of this silicate will then have to have the same properties as those described above for the alkaline metal silicates.
Surprisingly, the presence of saccharose having very great purity affects the life and setting times of the mixture but very little. The resistance to compression of the hardened mixture is higher than that obtained from known compositions and the subsequent destruction of the moulds and cores is substantially improved.
The hardener used in the composition of the present invention may be formed by a monoester and/or at least one polyester capable of releasing glycerol by saponification, in combination with a water-absorbent mono or polyalcohol branched or not, and having groups capable of accentuating its polarity, such as a mixture of triacetine-monoacetine and diethyleneglycol, or more advantageously by an ester or a mixture of cyclic or non-cyclic hydrolysable esters having 3 to 30 carbon atoms, such as alcohol and carbonic acid esters, and in particular ethylene carbonate, propylene carbonate or a mixture thereof.
Propylene carbonate gives a particularly favourable lifetime-setting time ratio to the silicated sands in which it is incorporated. If it is desired to reduce the setting the setting time, a mixture of ethylene carbonate and propylene carbonate may be advantageously used in adequate proportions by taking care to obtain an homogeneous solution before use.
Since these parameters vary depending on the temperature, it is desirable to use compositions appropriate to the summer-winter periods.
It will also be noted that the use of a hardener not releasing glycerine allows a sand to be obtained after regeneration containing very few fines and which for this reason does not adversely affect the life and setting times. The amount of hardener in relation to the sand is between 0.2 and 0.5% by weight.
It will generally be ten times smaller than the amount of the silicate and sugar solution also added to the moulding or coring sand.
As sugar for use in the composition of the invention, candi sugar may be mentioned which is obtained by slow crystallization and has a saccharose purity of 99.9%, and icing sugar obtained by crushing No. 1 refined crystallized sugar which also has a saccharose purity of 99.9%. It should be noted that icing sugar which sometimes contains up to 3% starch, is not suitable in the present invention, and that only non-starchy icing sugar allows a good result to be obtained.
The sugar is preferably directly mixed with the alkaline metal silicate. The amount of sugar in relation to that of the dry sodium, potassium and lithium silicates is respectively between 12.5 and 44%, 10 and 35%, and 17 and 60% by weight
The sugar may also be incorporated in the alkaline silicate solution. For example, the amount of sugar in relation to that of the sodium silicate solution is between 5 and 20% by weight. Care must be taken to obtain a perfect homogeneity of the silicate solution with the sugar.
The aqueous solution of alkaline metal silicate and sugar has a solid matter content between 40 and 55% by weight.
The amount of the sugar and silicate solution in relation to the sand is between 2 and 5% by weight.
The invention also provides a process for cold-hardening foundry sands by means of the above-described composition, in which the hardener will advantageously be a hardener not releasing glycerol, characterized in that the foundry sand is a new sand or regenerated sand coming from a sand already having been subjected to hardening by means of the composition of the invention.
By regenerated sand is meant a sand which comes from new sand, which has been coated during the first cycle, and in all the following cycles with the composition of the invention. This sand may in particular be a siliceous sand, or a usual refractory composition such as olivine, zircon, chromite... In practice, for smooth running of the shop, a store of sand is formed. At each cycle, the regenerated sand is completed with new sand so as to have the desired amount of sand. Regeneration is carried out with equipment currently used in foundries for this application.
The process of the invention allows sand to be reused; thus their discharge is avoided. It seems that the reuse of sand, previously bonded by the composition of the invention, is made possible because of a limitation of the reactivity of the residues on the surface of the grains of sand, residues which greatly disturb the mechanical characteristics of the moulds and cores during setting before each regeneration.
So as to obtain a sand whose mechanical characteristics, life and setting times are excellent and reproducible even after numerous regeneration cycles, the ingredients of the composition of the invention may advantageously be chosen.
Prefereably, the silicate is an alkaline metal (Me) silicate whose SiO2/Me2O weight (or modulus) is, when
Me represents sodium, potassium and lithium, respectively between 1.9-2.1; 1.25-1.37; and 3.95-4.30. An organic silicate may also be used having the same proprties, as far as its modulus is concerned, as the alkaline metal silicate.
The amount of sugar present in the composition for coating a regenerated sand is less than the amount of sugar present in the composition for coating new sand, i.e. during the first cycle.
In effect, it has been found that when the amount of sugar in the composition for a regenerated sand is too high, the setting of the mixture formed by the sand and the composition is not easily effected.
More precisely, in the composition used in the first cycle, the amount of sugar in relation to that of the dry sodium, potassium and lithium silicates is respectively from 33 to 44%, 26 to 35% and 45 to 60% by weight.
During the following cycles, the amount of sugar in relation to that of the dry sodium, potassium and lithium silicates is respectively between 12.5 and 17.6%, 10 and 14%, and 17 and 24.1% by weight.
The process of the present invention enables sand to be recycled at a rate easily reaching 90% by weight.
The portion of new sand added to each cycle is then about 10%. In fact, this rate of 10% corresponds to the loss of sand during regeneration, stripping, crushing, sifting, and transporting into storage silos. It appears then that the process of the invention provides optimum recycling.
The following examples illustrate the present invention.
Example 1
The four mixtures shown in Table I below were prepared for making foundry cores and moulds:
TABLE I
Composition of the mixtures A B C D
Siliceous sand 100 100 100 100
Polyester-triacetine/monoacetine 50-50 0.6 0.6 0.51 0.51
Initiator-diethyleneglycol 0.09 0.09
Saccharose 0.45 0.45
Sodium silicate 3 2.55 3 2.55
Mixture A with sodium silicate having a modulus 2.1
Mixtures B, C and D with sodium silicate having a modulus of 2.4
The values shown give percentages by weight.The lifetime, the setting time and the resistance to compression as a function of time, of mixtures A, B, C and Dare given in Table II below:
TABLE II
Mixture used A B C D
Lifetime 4' 4' 10' 15'
Setting time 20/25' 15' 45' 45'
Lifetime/Setting time 0.2/0.17' 0.266' 0.22' 0.33'
Resistance to compression - 6.4' - (kg/cm2) after: 15' 20' 5 7.5' -
30' 8 12.5 -
40' 12 13 5.5 6
45' > 13 > 13 7.2 7.5
50' > 13 > 13 9.7 10.5
60' > 13 > 13 10 12
It appears that mixtures B and D of the invention have very advantageous lifetime/setting time ratios and higher values insofar as resistance to compression is concerned. The destruction of the moulds obtained with mixtures B and D is also easier.
Example 2
Three compositions in accordance with the invention and shown in Table III below were prepared:
TABLE Ill
Composition of the mixtures E F G
New siliceous sand 100 10 10
Regeneration sand - 90 90
Propylene carbonate 0.3 0.3 0.225
Ethylene carbonate 0.075
Sodium silicate (modulas 2) 1.14 1.27 1.27
Non-starcy icing sugar 0.45 0.20 0.20
Water 1.41 1.93 1.93
The values shown give percentages by weight. Mixture EF which is very suitable for coating sand in the first cycle until a store of sand required for the smooth running of the shop has been formed, is modified after the first cycle.
Mixtures F and G which are very suitable for coating regenerated sand have different compositions depending on the temperature of the sands. Mixture F is used in the summer period, whereas mixture G is used in the winter period.
The lifetime, setting time and the resistance to compression as a function of time, of mixtures E, F and G are given in Table IV below:
TABLE IV
Mixtures No. of Life- Setting Resistance to compression Kg/cm2
cycles time time after a setting time of:
30' 60' 90' 120' 24h
E 1 10' 45' 6 14 20 28 36
F 2 12' 1hr15' 3 6.5 12 16 40
G 2 7' 45' 6 12 18 23 38
F 5 11' 1hr15' 3.5 7.8 13 16.5 44
F 10 10' 1hr15' 3 6 12.5 17.5 42
G 10 6'30" 45' 6 12.5 18.5 23 41
F 15 9' 1hr10' 3.2 7.5 12.7 17 43
F 20 12' lhr 3.9 8.5 14 19 48
F 25 9' 1hr 4 8.6 12 18 38
G 25 5' 40' 7 13 19 24 40
The regeneration of the sands is effected by mechanical separation.It follows from the results given in
Table IV that the mechanical characteristics of the sands coated in accordance with the process of the present invention are excellent and show no deterioration even after numerous regeneration cycles.
Example 3
Different mixtures were prepared, using sugars of different natures. These mixtures are given in Table V below:
TABLE V
Composition ofthe mixtures 1 2 3 4
New siliceous sand 100 100 100 100
Propylene carbonate 0.3 0.3 0.3 0.3
Dry sodium silicate (Modulus 2) 1.38 1.14 1.14 1.14
Less refined No. 2 crystallized sugar - 0.45 - Candi sugar - - 0.45
Icing sugar (No. 1 refined) - - - 0.45
Water 1.62 1.41 1.41 1.41
The influence of the nature of the sugars on the mechanical characteristics of the mixtures was studied.
The results are given in Table VI below:
TABLE VI
Mixtures Lifetime Resistance to compression Kg/cm2
after a setting time of: 30mn 60' 90' 120' 24h
1 8' 4 10 12 17 40
2 20' 1.5 7 11 13 28
3 10' 7 16 22 30 40
4 10' 6 14 20 28 36
It appears then that the results obtained with icing or candi sugar which have a very high saccharose purity are superior to those obtained with less refined crystallized sugar or without sugar.
Example 4
Different mixtures appearing in Table VII below were prepared, by varying the amount of sugar. (The values appearing in this table are percentages by weight).
TABLE VII
Composition ofthe mixtures 5 6 7 10 Newsiliceoussand 100 100 100 100
Propylene carbonate 0.3 0.3 0.3 0.3
Dry sodium silicate (Modulus 2) 1.14 1.14 1.14 1.14
Icing sugar 0.45 0.70 1.1 1.6
Water 1.41 1.41 1.41 1.41
The properties of the mixtures were tested. The results are given in Table VIII below:
TABLE VIII
Mixtures Lifetime Resistance to compression Kg/cm2 as
a function of the setting time:
30' 60' 90' 120' 24h
5 10 6 14 20 28 36
6 15 4 10 13 18 34
7 20 1.3 8.5 10 12 32
8 25 0.5 4 8.5 11 33
It can be seen from this table that too high a proportion of sugar is prejudicial to the mechanical properties ofthe mixtures.
Example 5
Different mixtures appearing in Table IX below were prepared, by varying the nature and the percentage of the silicate and the catalyst.
TABLE IX
Composition ofthe mixtures 9 10 11 12 13 14 15 16
New siliceous sand 10 10 10 10 10 10 10 10
Regenerated sand 90 90 90 90 90 90 90 90
Propylene carbonate 0.3 0.3 0.25 0.60 0.3 0.3 0.3 0.225
Ethylene carbonate - - - - - - - 0.075
Dry sodium silicate of - 1.27 1.27 1.27 1.12 1.28 1.27 1.27 modulus 2
Dry sodium silicate of 1.045 - - - - - - - modulus 2.4
Icing sugar 0.45 0.20 0.20 0.20 0.18 0.18 0.20 0.20
Water 1.505 1.93 1.93 1.93 1.70 2.3 1.93 1X93 The values given in the table are percentages by weight.
The mechanical properties of mixtures 9 to 16 were tested. The results are given in Table X below:
TABLE X
Mixture Lifetime Resistance to compression Kg/cm2
after a setting time of:
30' 60' 90' 120' 24h
9 IMMEDIATE SETTING IN THE MIXER 10 15' 3 6.5 12 16 40 11 18' 1.7 4 9 12 30 12 10' 5 7 13 18 38 13 6' 1.7 3.5 7 11 30 14 15' 5 9 14 18 44 15 15' 3 6.5 12 16 40 16 7' 6 12 18 23 38
The results obtained with mixtures 9 and 10 enable the influence of the modulus of the silicate to be established; the results obtained with mixtures 11 and 12 allow the influence of the percentage of the catalyst to be established; the results obtained with mixtures 13 and 14 allow the influence of the percentage of the silicate to be established; mixtures 15 and 16 describe respectively a hardener usable in summer and in winter.
The two preceding tables show that the hardening process for the regenerated sands of the invention requires the use of mixtures having a definite composition insofar as the modulus of the silicate, the percentage of the hardener and the percentage of the silicate are concerned.
Claims (17)
1. A composition for foundry sands formed from an aqueous solution of a silicate, a hardener and a sugar, wherein the sugar is a saccharose having a purity greater than 99.9%.
2. A composition as claimed in claim 1, wherein the silicate is an organic silicate obtained by reaction of silicic acid and an organic base.
3. A composition as claimed in claim 1, wherein the silicate is an alkaline metal (Me) silicate whose
SiO2/Me2O weight ratio is, when Me represents sodium, potassium and lithium, respectively between 1.9 and 2.4; 1.2 and 1.6; 3.9 and 5.
4. The composition as claimed in anyone of claims 1 to 3, wherein the hardener is a monoester and/or at least a polyester capable of releasing glycerol in combination with a water-absorbent mono or poly-alcohol.
5. The composition as claimed in anyone of claim 1 to 3, wherein the hardener is a cyclic or non-cyclic hydrolysable ester having from 3 to 30 carbon atoms.
6. The composition as claimed in claim 5, wherein the hardener is ethylene carbonate, propylene carbonate or a mixture thereof.
7. The composition as claimed in anyone of claims 1 to 6, wherein the amount of hardener in relation to the sand is between 0.2 and 0.5% by weight.
8. The composition as claimed in anyone of claims 1 to 7, wherein the sugar is candi sugar or non-starchy icing sugar.
9. The composition as claimed in anyone of claims 3 to 8, wherein the amount of sugar in relation to that of the sodium, potassium and lithium silicate is respectively from 12.5 to 44% 10 to 35% and 17 to 60% by weight.
10. The composition as claimed in anyone of claims 1 to 9, wherein the aqueous solution of silicate and sugar has a solid matter content between 40 and 55% by weight.
11. The composition as claimed in anyone of claims 1 to 10, wherein the amount of the whole of the sugar and silicate solution in relation to the sand is between 2 and 5 % by weight.
12. A process for cold-hardening foundry sands, by means of the composition according to anyone of claims 1 to 11, wherein the foundry sand is new sand and a regenerated sand coming from a sand already having been subjected to hardening by means of the composition according to anyone of claims 1 to 11.
13. The process as claimed in claim 12, wherein the alkaline metal (Me) silicate has an SiO2/Me2O weight ratio, when Me represents sodium, potassium and lithium, respectively between 1.9 and 2.1, 1.25 and 1.37, and 3.95 and 4.3.
14. The process as claimed in anyone of claims 12 and 13, wherein the amount of sugar present in the composition intended for regenerated sand is less than the amount of sugar present in the composition intended for new sand.
15. The process as claimed in anyone of claims 12 to 14, wherein, in the composition, the amount of sugar in relation to that of the dry sodium, potassium and lithium silicats is respectively between 33 and 44 %, 26 and 35 %, 45 and 60 % by weight, when the composition is used for hardening new sand.
16. The process as claimed in anyone of claims 12 to 14, wherein, when the binder is intended for hardening regenerated sand, the amount of sugar in relation to the dry sodium, potassium and lithium silicates is respectively between 12.5 and 17.6%,10 and 14%, 17 and 24.1 % by weight.
17. The process as claimed in anyone of claims 12, 13, 14 and 16, wherein the sand is formed from about 90 % by weight of regenerated sand, the rest being new sand.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7905969A FR2450649A1 (en) | 1979-03-08 | 1979-03-08 | COMPOSITION BASED ON SILICATE, HARDENER AND SUGAR AND ITS APPLICATION TO COLD HARDENING OF SANDS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2045777A true GB2045777A (en) | 1980-11-05 |
Family
ID=9222897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8007656A Withdrawn GB2045777A (en) | 1979-03-08 | 1980-03-06 | A silicate, hardener and sugar- based composition and the application thereof in the cold-hardening of sands |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS55122646A (en) |
| BE (1) | BE882100A (en) |
| DE (1) | DE3008857A1 (en) |
| ES (1) | ES8102485A1 (en) |
| FR (1) | FR2450649A1 (en) |
| GB (1) | GB2045777A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4983218A (en) * | 1989-09-11 | 1991-01-08 | Arco Chemical Technology, Inc. | Composition and method for hardening an aqueous alkali metal silicate solution |
| WO2014202042A1 (en) * | 2013-06-17 | 2014-12-24 | Ask Chemicals Gmbh | Lithium-containing molding material mixture based on an inorganic binder for producing molds and cores for metal casting |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3137046A (en) * | 1960-10-24 | 1964-06-16 | Int Minerals & Chem Corp | Foundry sand composition and method of preparation |
| GB1087767A (en) * | 1965-01-29 | 1967-10-18 | British Non Ferrous Metals Res | Improvements in and relating to foundry moulding sand compositions |
| GB1137703A (en) * | 1966-09-19 | 1968-12-27 | Foseco Int | Sand moulds and cores |
| GB1403781A (en) * | 1972-04-04 | 1975-08-28 | Foseco Int | Bonded particulate material |
| FR2183528A1 (en) * | 1972-05-08 | 1973-12-21 | Lubrefor Sa | Rapid setting foundry sand compsn - by in situ generation of glycerol from sodium silicate-polyester reaction |
| JPS5215456A (en) * | 1975-07-28 | 1977-02-05 | Nippon Aluminium Mfg | Method of d*c* positive polarity tig welding of aluminium and its alloy |
| GB1566417A (en) * | 1976-11-11 | 1980-04-30 | Foseco Int | Alkali metal silicate binder compositions |
-
1979
- 1979-03-08 FR FR7905969A patent/FR2450649A1/en active Granted
-
1980
- 1980-02-28 ES ES489040A patent/ES8102485A1/en not_active Expired
- 1980-03-06 BE BE0/199686A patent/BE882100A/en not_active IP Right Cessation
- 1980-03-06 GB GB8007656A patent/GB2045777A/en not_active Withdrawn
- 1980-03-07 JP JP2973180A patent/JPS55122646A/en active Pending
- 1980-03-07 DE DE19803008857 patent/DE3008857A1/en not_active Ceased
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4983218A (en) * | 1989-09-11 | 1991-01-08 | Arco Chemical Technology, Inc. | Composition and method for hardening an aqueous alkali metal silicate solution |
| WO2014202042A1 (en) * | 2013-06-17 | 2014-12-24 | Ask Chemicals Gmbh | Lithium-containing molding material mixture based on an inorganic binder for producing molds and cores for metal casting |
| US9968989B2 (en) | 2013-06-17 | 2018-05-15 | Ask Chemicals Gmbh | Lithium-containing molding material mixture based on an inorganic binder for producing molds and cores for metal casting |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2450649B1 (en) | 1982-11-05 |
| BE882100A (en) | 1980-09-08 |
| FR2450649A1 (en) | 1980-10-03 |
| JPS55122646A (en) | 1980-09-20 |
| ES489040A0 (en) | 1981-02-16 |
| ES8102485A1 (en) | 1981-02-16 |
| DE3008857A1 (en) | 1980-09-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |