US2375650A - Manufacture and production of artificial filaments, threads, films, and the like - Google Patents
Manufacture and production of artificial filaments, threads, films, and the like Download PDFInfo
- Publication number
- US2375650A US2375650A US469350A US46935042A US2375650A US 2375650 A US2375650 A US 2375650A US 469350 A US469350 A US 469350A US 46935042 A US46935042 A US 46935042A US 2375650 A US2375650 A US 2375650A
- Authority
- US
- United States
- Prior art keywords
- alginate
- solution
- threads
- filaments
- alkaline earth
- 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
Links
- 238000004519 manufacturing process Methods 0.000 title description 5
- 235000010443 alginic acid Nutrition 0.000 description 29
- 229920000615 alginic acid Polymers 0.000 description 29
- -1 alkali metal alginate Chemical class 0.000 description 25
- 239000000243 solution Substances 0.000 description 25
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 22
- 229940072056 alginate Drugs 0.000 description 18
- 239000000203 mixture Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000783 alginic acid Substances 0.000 description 11
- 229960001126 alginic acid Drugs 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 9
- 150000004781 alginic acids Chemical class 0.000 description 9
- 239000001110 calcium chloride Substances 0.000 description 9
- 229910001628 calcium chloride Inorganic materials 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 235000010410 calcium alginate Nutrition 0.000 description 8
- 239000000648 calcium alginate Substances 0.000 description 8
- 229960002681 calcium alginate Drugs 0.000 description 8
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical class [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 239000000728 ammonium alginate Substances 0.000 description 5
- 235000010407 ammonium alginate Nutrition 0.000 description 5
- KPGABFJTMYCRHJ-YZOKENDUSA-N ammonium alginate Chemical compound [NH4+].[NH4+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O KPGABFJTMYCRHJ-YZOKENDUSA-N 0.000 description 5
- 239000001099 ammonium carbonate Substances 0.000 description 5
- 235000012501 ammonium carbonate Nutrition 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 159000000011 group IA salts Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 241001474374 Blennius Species 0.000 description 1
- 241001534961 Calicium Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/04—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of alginates
Definitions
- This invention relates to the production of artificial filaments, threads, films and the like with a basis of alginic acid.
- Alginic acid when prepared from seaweed, is generally obtained in the form of its calcium salt, which is insoluble in water, and in order to obtain from this calcium alginate a solution which can be spun into filaments and threads, or converted into films, it has been customary to treat the calcium alginate with hydrochloric acid, and then to remove the soluble calcium chloride from the insoluble alginic acid, and thereafter to dissolve the alginic acid in caustic soda solution, thus obtaining a solutionof sodium alginate, which is viscous, and then to extrude this viscous solution, using the ordinary technique for the production of artificial threads, into a solution of a calcium salt,
- filaments, threads and films can be obtained by extruding into a suitable setting medium an aqueous solution of an alkali metal alginate containingin suspension 2, finely divided alkaline earth metal salt which is less soluble than the corresponding alkaline earth metal alginate.
- a suspension can be obtained for instance by treating an alkaline earth metal alginate, such for example as calcium alginate or barium or give rise to water-soluble salts.
- alkaline earth metal salts 01' which are soluble in water
- the filaments formed consist generally of a mixture of the alkaline earth metal alginate and alginic acid, while the alkali metal salt which was originally added to the alkaline earth metal alginate in order to obtain the spinning solution remains in solution in the spinning bath and is thereby eliminated from the filaments.
- a soluble alkaline earth salt such as calcium chloride.
- filaments of calcium alginate and alginic acid may be treated with a solution of calcium chloride containing calcium hydroxide or finely divided calcium carbonate.
- ammonium carbonate When ammonium carbonate is used according to the present invention to bring the alginic acid radical into solution the, suspension obtained may be extruded into air and as the filaments begin to dry, the ammonia tends to evaporate leaving the free alginic acid to react with the alkaline earth metal carbonate in the suspension. Carbon dioxide is evolved and the filaments are converted to the insoluble alkaline earth. metal alginate. Sometimes, the last traces of ammonia leave the filament very slowly, and in this case the completion ofthe conversion of the ammonium alginate to the alkline earth metal alginate may be hastened by treatment with a dilute solution of a salt of the same alkaline earth metal, or by treatment with steam.
- the filaments formed may, if desired, be exposed to the air to complete the volatilisation of the ammonia, or may be further treated with a solution of an alkaline earth metal salt to ensure complete conversion of the alginic acid to alkaline earth metal alginate.
- the process according to this invention presents advantages since it avoids the necessity of removing the alkaline earth metal from the alkaline earth metal alginate, which is employed as raw material, thus enabling the manufacture of filaments, threads, films and the like to dispense with a laborous process, before the extrusion process is carried out.
- Example 1 8.4 kilograms of calcium alginate containing 20 per cent of moisture are dissolved in 90 kilograms of water containing 1.90 kilograms of sodium carbonate and 0.5 kilogram of 40 per cent formaldehyde as preservative. The suspension obtained is subsequently extruded into a solu tion containing 5 per cent of calcium chloride and 0.25 per cent of hydrochloric acid. The filaments thus produced are then treated with 0.1 per cent of hydrochloric acid at centigrade for minutes, then with 0.75 per cent of hydrochloric acid for 15 minutes and finally. for 15 minutes with 5 per cent of calcium chloride saturated with calcium hydroxide. The filaments are then washed and dried.
- Example 2 '7 kilograms of calicium alginate, 2.05 kilograms of ammonium carbonate, 0.6 kilogram of 0.880 ammonia and 90.35 kilograms of water are mixed for four hours at the ordinary temperature. The solution is then extruded through a suitable jet into a bath containing 5 per cent of calcium chloride. The threads thus formed are treated for 10 minutes with a saturated solution of calcium hydroxide, washed and dried.
- a process for producing artificial filaments, threads, films and the like which consists in reacting an alkaline earth metal alginate with an aqueous solution of an alkali metal salt thereby producing a mixture comprising a solution of alkali metal alginate in water having therein finely divided particles of alkaline earth metal salt, and extruding said mixture into a setting medium.
- threads, films and the like which consists in reacting an alkaline earth metal alginate with an aqueous solution or an alkali metal salt thereby producing a mixture comprising a solution of alkali metal alginate in water having therein finely divided particles of alkaline earth metal salt, and extruding said mixture into a setting medium containing an acid the alkaline salts of which are soluble in water.
- a process for producing artificial filaments, threads, films and the like which consists in reacting an alkaline earth metal alginate with an aqueous solution of ammonium carbonate therebyproducing a mixture comprising a solution of ammonium alginate in water having therein finely divided particles of alkaline earth metal carbonate, and extruding said mixture into a setting medium.
- a process for producing artificial filaments, threads, films and the like which consists in reacting calcium alginate with an aqueous solution of sodium carbonate thereby producing a mixture comprising a, solution of sodium alginate in water having therein finely divided particles of calcium carbonate, and extruding said mixture into a setting medium.
- threads, films and the like which consists in reacting calclum alginate with an aqueous solution of ammonium carbonate thereby producing a mixture comprising a solution of ammonium alginate in water having therein finely divided particles of calcium carbonate, and extruding said mixture into a setting medium.
- a process for producing artificial filaments, threads, films and the like which consists in reacting calcium alginate with an aqueous solution of ammonium carbonate thereby producing a.
- mixture comprising a solution of ammonium alginate in water having therein finely divided particles of calcium carbonate, and extruding said mixture into a setting medium containing an acid and about 5% calcium chloride, the alkaline salts of said acid being soluble in water.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
Description
Patented May 8, 1945 FICIAL FILAMENTS, THREADS,
AND THE LIKE FILMS,
Horace James Hegan and John Harrison Givens, Coventry, England, asslg'nors to Courtaulds Limited, London, England, a company of Great Britain No Drawing. Application December 17, 1942, Se-
rial No. 469,350. In Great Britain January 20,
7 Claims.
This invention relates to the production of artificial filaments, threads, films and the like with a basis of alginic acid. Alginic acid, when prepared from seaweed, is generally obtained in the form of its calcium salt, which is insoluble in water, and in order to obtain from this calcium alginate a solution which can be spun into filaments and threads, or converted into films, it has been customary to treat the calcium alginate with hydrochloric acid, and then to remove the soluble calcium chloride from the insoluble alginic acid, and thereafter to dissolve the alginic acid in caustic soda solution, thus obtaining a solutionof sodium alginate, which is viscous, and then to extrude this viscous solution, using the ordinary technique for the production of artificial threads, into a solution of a calcium salt,
whereupon threads or filaments of insoluble calcium alginate are produced. It has also been proposed to dissolve al'ginic acid in a mixture of caustic soda and ammonia, and to spin the solution thus obtained into a solution of calcium chloride, or to form a film of the solution by drying it on a glass plate, and then to render the film insoluble by treatment with a solution of calcium chloride.
We have now found that filaments, threads and films, all of which we will hereinafter include under the term filaments, can be obtained by extruding into a suitable setting medium an aqueous solution of an alkali metal alginate containingin suspension 2, finely divided alkaline earth metal salt which is less soluble than the corresponding alkaline earth metal alginate. Such a suspension can be obtained for instance by treating an alkaline earth metal alginate, such for example as calcium alginate or barium or give rise to water-soluble salts. Although there may theoretically be sufficient alkaline earth metal present to combine with the whole alginate, with a solution of a salt of an alkali may be extruded through a nozzle adapted to bring the solution into the desired shape into a setting bath containing a dilute acid, such as hydrochloric acid or acetic acid, the alkaline earth metal salts 01' which are soluble in water,
of the alginic acid, the filaments formed consist generally of a mixture of the alkaline earth metal alginate and alginic acid, while the alkali metal salt which was originally added to the alkaline earth metal alginate in order to obtain the spinning solution remains in solution in the spinning bath and is thereby eliminated from the filaments. We generally prefer to extrude the suspension into a setting bath containing both acid and also a soluble alkaline earth salt, such as calcium chloride. In order to ensure that the filaments are completely converted to the alkaline earth metal alginate we can subject them to further treatment with an alkaline earth metal compound. For example, filaments of calcium alginate and alginic acid may be treated with a solution of calcium chloride containing calcium hydroxide or finely divided calcium carbonate.
When ammonium carbonate is used according to the present invention to bring the alginic acid radical into solution the, suspension obtained may be extruded into air and as the filaments begin to dry, the ammonia tends to evaporate leaving the free alginic acid to react with the alkaline earth metal carbonate in the suspension. Carbon dioxide is evolved and the filaments are converted to the insoluble alkaline earth. metal alginate. Sometimes, the last traces of ammonia leave the filament very slowly, and in this case the completion ofthe conversion of the ammonium alginate to the alkline earth metal alginate may be hastened by treatment with a dilute solution of a salt of the same alkaline earth metal, or by treatment with steam. When the suspension containing ammonium alginate and alkaline earth metal carbonate has been extruded into an acidified spinnin bath the filaments formed may, if desired, be exposed to the air to complete the volatilisation of the ammonia, or may be further treated with a solution of an alkaline earth metal salt to ensure complete conversion of the alginic acid to alkaline earth metal alginate.
If, when carrying out the process of this in- Vention an alkali metal carbonate is used for bringing the alginic acid radical into solution, and it be desired, during the extrusion into an acidified bath to avoid the formation of bubbles in the filaments, the temperature and acidity of the bath into which the suspension is extruded should be kept sufficiently low.
The process according to this invention presents advantages since it avoids the necessity of removing the alkaline earth metal from the alkaline earth metal alginate, which is employed as raw material, thus enabling the manufacture of filaments, threads, films and the like to dispense with a laborous process, before the extrusion process is carried out.
The following examples serve to illustrate the nature of this invention which however is not limited to these examples:
Example 1 8.4 kilograms of calcium alginate containing 20 per cent of moisture are dissolved in 90 kilograms of water containing 1.90 kilograms of sodium carbonate and 0.5 kilogram of 40 per cent formaldehyde as preservative. The suspension obtained is subsequently extruded into a solu tion containing 5 per cent of calcium chloride and 0.25 per cent of hydrochloric acid. The filaments thus produced are then treated with 0.1 per cent of hydrochloric acid at centigrade for minutes, then with 0.75 per cent of hydrochloric acid for 15 minutes and finally. for 15 minutes with 5 per cent of calcium chloride saturated with calcium hydroxide. The filaments are then washed and dried.
Example 2 '7 kilograms of calicium alginate, 2.05 kilograms of ammonium carbonate, 0.6 kilogram of 0.880 ammonia and 90.35 kilograms of water are mixed for four hours at the ordinary temperature. The solution is then extruded through a suitable jet into a bath containing 5 per cent of calcium chloride. The threads thus formed are treated for 10 minutes with a saturated solution of calcium hydroxide, washed and dried.
What we claim is:
l. A process for producing artificial filaments, threads, films and the like which consists in reacting an alkaline earth metal alginate with an aqueous solution of an alkali metal salt thereby producing a mixture comprising a solution of alkali metal alginate in water having therein finely divided particles of alkaline earth metal salt, and extruding said mixture into a setting medium.
2. A process for producing artificial filaments.
threads, films and the like which consists in reacting an alkaline earth metal alginate with an aqueous solution or an alkali metal salt thereby producing a mixture comprising a solution of alkali metal alginate in water having therein finely divided particles of alkaline earth metal salt, and extruding said mixture into a setting medium containing an acid the alkaline salts of which are soluble in water.
3. A process for producing artificial filaments, threads, films and the like as claimed in claim 2, in which the setting medium contains a watersoluble alkaline earth metal salt.
4. A process for producing artificial filaments, threads, films and the like, which consists in reacting an alkaline earth metal alginate with an aqueous solution of ammonium carbonate therebyproducing a mixture comprising a solution of ammonium alginate in water having therein finely divided particles of alkaline earth metal carbonate, and extruding said mixture into a setting medium.
5. A process for producing artificial filaments, threads, films and the like, which consists in reacting calcium alginate with an aqueous solution of sodium carbonate thereby producing a mixture comprising a, solution of sodium alginate in water having therein finely divided particles of calcium carbonate, and extruding said mixture into a setting medium.
6. A process for producing artificial filaments.
threads, films and the like, which consists in reacting calclum alginate with an aqueous solution of ammonium carbonate thereby producing a mixture comprising a solution of ammonium alginate in water having therein finely divided particles of calcium carbonate, and extruding said mixture into a setting medium.
7. A process for producing artificial filaments, threads, films and the like,.which consists in reacting calcium alginate with an aqueous solution of ammonium carbonate thereby producing a.
mixture comprising a solution of ammonium alginate in water having therein finely divided particles of calcium carbonate, and extruding said mixture into a setting medium containing an acid and about 5% calcium chloride, the alkaline salts of said acid being soluble in water.
HORACE JAMES HEGAN. JOHN HARRISON GIVENS.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB2375650X | 1942-01-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2375650A true US2375650A (en) | 1945-05-08 |
Family
ID=10905132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US469350A Expired - Lifetime US2375650A (en) | 1942-01-20 | 1942-12-17 | Manufacture and production of artificial filaments, threads, films, and the like |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2375650A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2512616A (en) * | 1946-01-12 | 1950-06-27 | Johnson & Johnson | Hemostatic alginic surgical dressings |
| US2542052A (en) * | 1947-06-10 | 1951-02-20 | Harry S Owens | Polyvalent metal pectinate films and process of producing same |
| US3345215A (en) * | 1963-03-16 | 1967-10-03 | Varta Pertrix Union Gmbh | Separator for primary cells |
| US4562110A (en) * | 1981-08-18 | 1985-12-31 | Tong David Philip | Process for the production of alginate fibre material and products made therefrom |
-
1942
- 1942-12-17 US US469350A patent/US2375650A/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2512616A (en) * | 1946-01-12 | 1950-06-27 | Johnson & Johnson | Hemostatic alginic surgical dressings |
| US2542052A (en) * | 1947-06-10 | 1951-02-20 | Harry S Owens | Polyvalent metal pectinate films and process of producing same |
| US3345215A (en) * | 1963-03-16 | 1967-10-03 | Varta Pertrix Union Gmbh | Separator for primary cells |
| US4562110A (en) * | 1981-08-18 | 1985-12-31 | Tong David Philip | Process for the production of alginate fibre material and products made therefrom |
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