US2154893A - Manufacture of artificial threads or the like - Google Patents
Manufacture of artificial threads or the like Download PDFInfo
- Publication number
- US2154893A US2154893A US64084A US6408436A US2154893A US 2154893 A US2154893 A US 2154893A US 64084 A US64084 A US 64084A US 6408436 A US6408436 A US 6408436A US 2154893 A US2154893 A US 2154893A
- Authority
- US
- United States
- Prior art keywords
- threads
- spinning
- viscose
- thread
- bath
- 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 4
- 238000009987 spinning Methods 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 14
- 229920000297 Rayon Polymers 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000003204 osmotic effect Effects 0.000 description 3
- 230000005070 ripening Effects 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- HFMDLUQUEXNBOP-UHFFFAOYSA-N n-[4-amino-1-[[1-[[4-amino-1-oxo-1-[[6,9,18-tris(2-aminoethyl)-15-benzyl-3-(1-hydroxyethyl)-12-(2-methylpropyl)-2,5,8,11,14,17,20-heptaoxo-1,4,7,10,13,16,19-heptazacyclotricos-21-yl]amino]butan-2-yl]amino]-3-hydroxy-1-oxobutan-2-yl]amino]-1-oxobutan-2-yl] Chemical compound OS(O)(=O)=O.N1C(=O)C(CCN)NC(=O)C(NC(=O)C(CCN)NC(=O)C(C(C)O)NC(=O)C(CCN)NC(=O)CCCCC(C)CC)CCNC(=O)C(C(C)O)NC(=O)C(CCN)NC(=O)C(CCN)NC(=O)C(CC(C)C)NC(=O)C1CC1=CC=CC=C1 HFMDLUQUEXNBOP-UHFFFAOYSA-N 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
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
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/06—Preparation of sulfur; Purification from non-gaseous sulfides or materials containing such sulfides, e.g. ores
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/48—Sulfur dioxide; Sulfurous acid
- C01B17/50—Preparation of sulfur dioxide
- C01B17/52—Preparation of sulfur dioxide by roasting sulfides
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B13/00—Fertilisers produced by pyrogenic processes from phosphatic materials
- C05B13/02—Fertilisers produced by pyrogenic processes from phosphatic materials from rock phosphates
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/10—Roasting processes in fluidised form
-
- 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
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
Definitions
- Our present invention relates to the manufacture of artificial threads or the like.
- One of its objects is to provide an improved process of producing artificial threads films or 5 the like from viscose. Further objects will be seen from the detailed specification following hereafter.
- films, threads and the like having a very high tensile strength in the wet state and also good extensibility may be produced from viscose if the viscose has been ripened so far as to have an ammonium chloride number below 7 to 6 (Hottenroth number).
- the thread In order to obtain the above effect, the thread must be subjected to tension in a water bath or a bath containing an electrolyte in strong dilution immediately following the coagulation before any or only after traces of cellulose have been regenerated, that is to say while the thread still consists in the main part of xanthogenate. It is essential that the decomposition of the xanthogenate takes place only after the application of tension.
- sufuric acid is suitable.
- the extension of the coagulated material may be carried out while the material dips into water or in water containing a small quantity of electrolyte.
- the pH-value of this bath may have the same values as the 5 spinning bath, however, it may be even less than one, so as to correspond with a sulfuric acid content of 1-2%, that is to say, to a pH-value of about 0.8.
- the'temperature of the water is preferably about 20 C.; if the viscose has been more strongly ripened it is possible to spin even with water of 0 C. If the viscose has been less ripened the spinning bath may have a temperature of 25 C. and more.
- the bath in which the tension is applied contains preferably traces or a small quantity of electrolyte in order to avoid sticking of the single fibers (for instance, there is used sulfuric acid of 1 to 2 per cent).
- Thetension which is applied to the thread may be produced in various manner, for instance, by bending the thread so that no essential permanent extension of the thread occurs.
- the xanthogenate After having exposed the thread to thetension for producing the high tensile strength in the wet state the xanthogenate is decomposed in the usual manner by means of dilute sulfuric acid with or without the addition of salt whereby lesser concentrations of the decomposing bath than usual may be applied because of the' strong self-decomposition of the xanthogenate due to the extremely strong ripening of the viscose.
- the viscose enters at l into a spinning head and is guided to the spinning nozfile 2.
- the precipitating liquid enters the spinning head through 40 the tube 3 and flows through the spinning funnel 4.
- the viscose is coagulated.
- the thread 8 enters a bath 1 in which rods 9 are provided for imparting tension to the thread 8.
- Example 2 When operating as described in Example 1 but bending the thread 4 times for applying tension there is obtained a material which has the same titer as the thread obtained according to Example 1, however it has the following properties:
- a process of producing artificial film threads and the like of high tensile strength which comprises coagulating viscose having a degree of ripening corresponding with an ammosure of which corresponds at most with thatof an aqueous solution of 1 per cent of sodium suifate and 0.2 per cent of sulfuric acid, said solu-- tion having a pH-value of between 0.8 and 11 while avoiding material permanent extension. and decomposing the material to cellulose hydrate after the applicaiton of tension.
- a process of producing artificial iilms, threads and the like of high tensile strength which comprises coagulating viscose having a degree of ripening corresponding with an ammonium chloride number below 7 in an aqueous spinning bath having a pH-value of 1.0 to 11 and an osmotic pressure corresponding at most with that of an aqueous solution of 1% of sodium sulfate and 0.2% of sulfuric acid to form xanthogenate containing at most traces of regenerated cellulose, subjecting the coagulated material to tension in an aqueous liquid having a pH-value of 0.8 to 11 and an osmotic pressure corresponding at most with that of an aqueous solution of 1% of sodium sulfate and 2% of sulfuric acid while, avoiding material permanent extension, and decomposing the material to cellulose hydrate after the application of tension.
- a process of producing artificial threads of high tensile strength which comprises spinning viscose having a degree of ripeness corresponding with an ammonium chloride number of 1.4 into a spinning bath of water heated at 22 C. and circulated through a spinning funnel, guiding the spinning bath and the threads into a vessel, mixing said spinning bath with sulfuric acid to have a pH-value of about 2, applying stretch to said threads while in said mixture of sulfuric acid with the spinning bath and winding the threads on a receiving device, while treating them with acid.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Description
April 1939- o. EISENHUT ET AL 2,154,893
MANUFACTURE OF ARTIFICIAL THREADS OR THE LIKE Filed Feb. 15, 1936' In ven fors By mo r Afforneys Patented Apr. 18, 1939 UNITED STATES PATENT oFFloE MANUFACTURE OF ARTIFICIAL THREADS OR THE LIKE Application February 15, 1936, Serial No. 64,084 In Germany February 15, 1935.
3 Claims.
Our present invention relates to the manufacture of artificial threads or the like.
One of its objects is to provide an improved process of producing artificial threads films or 5 the like from viscose. Further objects will be seen from the detailed specification following hereafter.
It is known that films, threads and the like made from viscose and not subjected to a special aftertreatment have comparatively little strength in wet condition. It has been attempted to increase the wet tenacity of such materials by sub stituting for the aftertreatment the use of more expensive highly concentrated baths accompanied by stretching, whereby the dry tenacity is increased; however, this process considerably diminishes the extensibility of the material. Moreover, use of highly concentrated baths in itself involves certain technical difficulties and the baths attack cellulose material so that the stability of the material is damaged.
According to this invention we have found that films, threads and the like having a very high tensile strength in the wet state and also good extensibility, may be produced from viscose if the viscose has been ripened so far as to have an ammonium chloride number below 7 to 6 (Hottenroth number). In order to obtain the above effect, the thread must be subjected to tension in a water bath or a bath containing an electrolyte in strong dilution immediately following the coagulation before any or only after traces of cellulose have been regenerated, that is to say while the thread still consists in the main part of xanthogenate. It is essential that the decomposition of the xanthogenate takes place only after the application of tension.
In this manner there is obtained a very homogeneous material which, in the case of thread material, has a substantially cylindrical cross section and does not show even under the highest magnification any or scarcely any difference of structure throughout the whole cross section. If the tension is applied too early, that is to say during the coagulation, then the desired properties are produced to a feeble degree or not at all. The viscose may be coagulated in the manner described in U. S. Patent No. 2,065,175 by means of water without any addition or with addition of a. small quantity of a substance which assists coagulation, while avoiding the use of expensive precipitating baths. Thus a spinning bath having a pH-value of 1.0 to 11 and an osmotic pressure corresponding at most with that of an aqueous solution of 1% of sodium sulfate and 0.2%
of sufuric acid is suitable. The extension of the coagulated material may be carried out while the material dips into water or in water containing a small quantity of electrolyte. The pH-value of this bath may have the same values as the 5 spinning bath, however, it may be even less than one, so as to correspond with a sulfuric acid content of 1-2%, that is to say, to a pH-value of about 0.8.
With a degree of ripeness corresponding with 19 a Hottenroth number of 2 to 1 the'temperature of the water is preferably about 20 C.; if the viscose has been more strongly ripened it is possible to spin even with water of 0 C. If the viscose has been less ripened the spinning bath may have a temperature of 25 C. and more. When spinning threads the bath in which the tension is applied contains preferably traces or a small quantity of electrolyte in order to avoid sticking of the single fibers (for instance, there is used sulfuric acid of 1 to 2 per cent). Thetension which is applied to the thread may be produced in various manner, for instance, by bending the thread so that no essential permanent extension of the thread occurs. After having exposed the thread to thetension for producing the high tensile strength in the wet state the xanthogenate is decomposed in the usual manner by means of dilute sulfuric acid with or without the addition of salt whereby lesser concentrations of the decomposing bath than usual may be applied because of the' strong self-decomposition of the xanthogenate due to the extremely strong ripening of the viscose.
In the accompanying drawing there is shown an arrangement for spinning in accordance with the invention.
The viscose enters at l into a spinning head and is guided to the spinning nozfile 2. The precipitating liquid enters the spinning head through 40 the tube 3 and flows through the spinning funnel 4. In the spinning funnel the viscose is coagulated. When leaving the spinning funnel 4 the thread 8 enters a bath 1 in which rods 9 are provided for imparting tension to the thread 8.
grams per denier wet, with an extension of 16 per cent. and 18 per cent. respectively. Artificial having 90 perforations, each 0.8 mm. wide, into 7 a funnel 55 cms. long, the speed of draft being 50 meters per minute and the precipitating bath being water at 22 0.; directly after leaving the funnel the thread and the precipitating water pass into a vessel into which acid has been added, drop by drop, so that the liquid has a pH-value of about 2. For the purpose of producing a tension the thread is guided over rods to the bottom of the vessel and then up again and finally wound on a reel, while being treated with acid.
The threads thus obtained and having a titer of 3.5 show the following data:
Dry tenacity grams per denier..- 2.5- 2.6 Wet tenacity do 1.8- 1.9 Extension, dry per cent 15.3 Extension, wet do 16.2
Example 2.When operating as described in Example 1 but bending the thread 4 times for applying tension there is obtained a material which has the same titer as the thread obtained according to Example 1, however it has the following properties:
Tensile strength in the dry state gr./denier 2.8 Tensile strength in the wet state do 2.3 Extensibility in the dry state per cent 10.5 Extensibility in the wet state do 10.1
. What we claim is:
1. A process of producing artificial film threads and the like of high tensile strength which comprises coagulating viscose having a degree of ripening corresponding with an ammosure of which corresponds at most with thatof an aqueous solution of 1 per cent of sodium suifate and 0.2 per cent of sulfuric acid, said solu-- tion having a pH-value of between 0.8 and 11 while avoiding material permanent extension. and decomposing the material to cellulose hydrate after the applicaiton of tension.
2. A process of producing artificial iilms, threads and the like of high tensile strength which comprises coagulating viscose having a degree of ripening corresponding with an ammonium chloride number below 7 in an aqueous spinning bath having a pH-value of 1.0 to 11 and an osmotic pressure corresponding at most with that of an aqueous solution of 1% of sodium sulfate and 0.2% of sulfuric acid to form xanthogenate containing at most traces of regenerated cellulose, subjecting the coagulated material to tension in an aqueous liquid having a pH-value of 0.8 to 11 and an osmotic pressure corresponding at most with that of an aqueous solution of 1% of sodium sulfate and 2% of sulfuric acid while, avoiding material permanent extension, and decomposing the material to cellulose hydrate after the application of tension.
3. A process of producing artificial threads of high tensile strength which comprises spinning viscose having a degree of ripeness corresponding with an ammonium chloride number of 1.4 into a spinning bath of water heated at 22 C. and circulated through a spinning funnel, guiding the spinning bath and the threads into a vessel, mixing said spinning bath with sulfuric acid to have a pH-value of about 2, applying stretch to said threads while in said mixture of sulfuric acid with the spinning bath and winding the threads on a receiving device, while treating them with acid.
' O'ITO EISENHUT.
HANNS REIN. HUGO WIDMANN.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE185649X | 1933-10-10 | ||
| DE2154893X | 1935-02-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2154893A true US2154893A (en) | 1939-04-18 |
Family
ID=32070559
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US747646A Expired - Lifetime US2065175A (en) | 1933-10-10 | 1934-10-09 | Manufacture of artificial silk |
| US64084A Expired - Lifetime US2154893A (en) | 1933-10-10 | 1936-02-15 | Manufacture of artificial threads or the like |
| US83158A Expired - Lifetime US2155934A (en) | 1933-10-10 | 1936-06-02 | Manufacture of artificial silk |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US747646A Expired - Lifetime US2065175A (en) | 1933-10-10 | 1934-10-09 | Manufacture of artificial silk |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US83158A Expired - Lifetime US2155934A (en) | 1933-10-10 | 1936-06-02 | Manufacture of artificial silk |
Country Status (7)
| Country | Link |
|---|---|
| US (3) | US2065175A (en) |
| BE (4) | BE405431A (en) |
| CH (6) | CH185649A (en) |
| DE (2) | DE738486C (en) |
| FR (7) | FR778985A (en) |
| GB (6) | GB443971A (en) |
| NL (6) | NL39054C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2461094A (en) * | 1944-04-12 | 1949-02-08 | American Viscose Corp | Method of making lightweight filamentous structures |
| US2727274A (en) * | 1953-02-16 | 1955-12-20 | Harry A Kuljian | Synthetic thread manufacturing apparatus |
| US4159299A (en) * | 1976-04-06 | 1979-06-26 | Serkov Arkady T | Method for the production of rayon |
| US20030098527A1 (en) * | 2000-03-06 | 2003-05-29 | Tei Biosciences, Inc. | Method and apparatus for biopolymer coagulation in a uniform flow |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE743851C (en) * | 1940-04-12 | 1944-01-04 | Deutsches Forschungsinstitut F | Process for the production of cellulose threads from well-ripened viscose |
| DE845231C (en) * | 1943-08-07 | 1952-07-31 | Glanzstoff Ag | Process for the direct production of a warpable and wool-like staple fiber tape with a good surface quality of the fibers from viscose |
| BE508100A (en) * | 1951-12-07 | |||
| FR1337249A (en) * | 1962-05-16 | 1963-09-13 | Cta Cie Ind De Textiles Artifi | Method and device for the manufacture of fancy yarns |
| SE323504B (en) * | 1966-10-17 | 1970-05-04 | F Haegeby | |
| US4409384A (en) | 1981-11-12 | 1983-10-11 | E. I. Du Pont De Nemours And Company | Viscose preparation using low concentration caustic |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE157157C (en) * | ||||
| DE402405C (en) * | 1918-02-23 | 1924-09-15 | Glanzfaeden Akt Ges | Process for the production of a wool-like web from viscose solutions |
| DE389394C (en) * | 1918-02-23 | 1924-01-31 | Glanzfaeden Ag | Process for the production of a wool-like web from viscose solutions |
| DE431846C (en) * | 1922-11-16 | 1926-07-16 | Adolf Kaempf Dr | Process for the production of rayon, synthetic fibers, films, ribbons etc. from viscose |
| DE445445C (en) * | 1923-08-20 | 1927-06-11 | I G Farbenindustrie Akt Ges | Process for the production of fine-grained viscose silk |
| AT108122B (en) * | 1926-03-08 | 1927-11-25 | Ig Farbenindustrie Ag | Process for the production of synthetic fiber, rayon, artificial horsehair, artificial straw, artificial tubes, ribbons, films and the like from viscose. |
| GB279888A (en) * | 1926-10-30 | 1929-04-29 | Ig Farbenindustrie Ag | Improvements in spinning artificial silk |
| US1857948A (en) * | 1929-04-12 | 1932-05-10 | Int Paper Canada | Process of preparing cellulose xanthate |
-
0
- BE BE429332D patent/BE429332A/xx unknown
- BE BE415801D patent/BE415801A/xx unknown
- BE BE413845D patent/BE413845A/xx unknown
-
1933
- 1933-10-11 DE DEI48091D patent/DE738486C/en not_active Expired
-
1934
- 1934-09-10 GB GB25955/34A patent/GB443971A/en not_active Expired
- 1934-09-26 CH CH185649D patent/CH185649A/en unknown
- 1934-09-28 BE BE405431D patent/BE405431A/xx unknown
- 1934-09-28 NL NL70892A patent/NL39054C/xx active
- 1934-09-28 FR FR778985D patent/FR778985A/en not_active Expired
- 1934-10-09 US US747646A patent/US2065175A/en not_active Expired - Lifetime
-
1935
- 1935-03-28 GB GB9681/35A patent/GB456061A/en not_active Expired
- 1935-07-19 GB GB20593/35A patent/GB460026A/en not_active Expired
- 1935-10-12 DE DEI53385D patent/DE746991C/en not_active Expired
- 1935-12-16 GB GB34871/35A patent/GB467426A/en not_active Expired
- 1935-12-16 GB GB34872/35A patent/GB467427A/en not_active Expired
-
1936
- 1936-01-27 NL NL76327A patent/NL41213C/xx active
- 1936-01-31 FR FR46999D patent/FR46999E/en not_active Expired
- 1936-02-10 CH CH217931D patent/CH217931A/en unknown
- 1936-02-15 US US64084A patent/US2154893A/en not_active Expired - Lifetime
- 1936-05-28 FR FR47396D patent/FR47396E/en not_active Expired
- 1936-05-28 NL NL77963A patent/NL42623C/xx active
- 1936-06-02 US US83158A patent/US2155934A/en not_active Expired - Lifetime
- 1936-06-03 CH CH220402D patent/CH220402A/en unknown
- 1936-10-10 FR FR47945D patent/FR47945E/en not_active Expired
- 1936-11-09 FR FR47950D patent/FR47950E/en not_active Expired
- 1936-11-10 FR FR47951D patent/FR47951E/en not_active Expired
- 1936-11-11 NL NL79965A patent/NL45097C/xx active
- 1936-11-12 CH CH218807D patent/CH218807A/en unknown
- 1936-11-12 CH CH218808D patent/CH218808A/en unknown
-
1937
- 1937-09-18 GB GB25377/37A patent/GB502858A/en not_active Expired
-
1938
- 1938-07-02 NL NL88640A patent/NL49792C/xx active
- 1938-07-04 CH CH223197D patent/CH223197A/en unknown
- 1938-07-22 FR FR49644D patent/FR49644E/en not_active Expired
-
1952
- 1952-04-22 NL NL168962A patent/NL79966C/xx active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2461094A (en) * | 1944-04-12 | 1949-02-08 | American Viscose Corp | Method of making lightweight filamentous structures |
| US2727274A (en) * | 1953-02-16 | 1955-12-20 | Harry A Kuljian | Synthetic thread manufacturing apparatus |
| US4159299A (en) * | 1976-04-06 | 1979-06-26 | Serkov Arkady T | Method for the production of rayon |
| US20030098527A1 (en) * | 2000-03-06 | 2003-05-29 | Tei Biosciences, Inc. | Method and apparatus for biopolymer coagulation in a uniform flow |
| US6705850B1 (en) * | 2000-03-06 | 2004-03-16 | Tei Biosciences, Inc. | Apparatus for biopolymer coagulation in a uniform flow |
| US6875397B2 (en) | 2000-03-06 | 2005-04-05 | Tei Biosciences, Inc. | Methods for biopolymer coagulation |
Also Published As
| Publication number | Publication date |
|---|---|
| NL39054C (en) | 1936-09-15 |
| CH185649A (en) | 1936-08-15 |
| FR47945E (en) | 1937-08-23 |
| DE738486C (en) | 1943-08-18 |
| NL45097C (en) | 1939-02-15 |
| NL42623C (en) | 1938-02-15 |
| FR47951E (en) | 1937-08-28 |
| FR46999E (en) | 1936-11-23 |
| FR49644E (en) | 1939-05-16 |
| DE746991C (en) | 1944-09-04 |
| BE415801A (en) | |
| FR778985A (en) | 1935-03-27 |
| CH218808A (en) | 1941-12-31 |
| CH217931A (en) | 1941-11-15 |
| GB456061A (en) | 1936-10-28 |
| FR47950E (en) | 1937-08-23 |
| CH223197A (en) | 1942-08-31 |
| BE413845A (en) | |
| NL79966C (en) | 1955-12-15 |
| GB502858A (en) | 1939-03-20 |
| NL49792C (en) | 1941-01-15 |
| BE405431A (en) | 1934-10-31 |
| CH220402A (en) | 1942-03-31 |
| GB467427A (en) | 1937-06-16 |
| US2065175A (en) | 1936-12-22 |
| GB443971A (en) | 1936-03-10 |
| NL41213C (en) | 1937-07-15 |
| CH218807A (en) | 1941-12-31 |
| BE429332A (en) | |
| US2155934A (en) | 1939-04-25 |
| GB467426A (en) | 1937-06-16 |
| FR47396E (en) | 1937-03-25 |
| GB460026A (en) | 1937-01-19 |
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