CA2012263C - Article coated with cured material and methods of making - Google Patents
Article coated with cured material and methods of makingInfo
- Publication number
- CA2012263C CA2012263C CA002012263A CA2012263A CA2012263C CA 2012263 C CA2012263 C CA 2012263C CA 002012263 A CA002012263 A CA 002012263A CA 2012263 A CA2012263 A CA 2012263A CA 2012263 C CA2012263 C CA 2012263C
- Authority
- CA
- Canada
- Prior art keywords
- cure
- probe
- degree
- coating
- curable
- 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 - Fee Related
Links
- 239000000463 material Substances 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title claims description 23
- 239000011248 coating agent Substances 0.000 claims abstract description 114
- 238000000576 coating method Methods 0.000 claims abstract description 114
- 239000011159 matrix material Substances 0.000 claims abstract description 91
- 239000013307 optical fiber Substances 0.000 claims abstract description 61
- 239000000470 constituent Substances 0.000 claims abstract description 16
- 239000000523 sample Substances 0.000 claims description 71
- 230000003287 optical effect Effects 0.000 claims description 15
- 230000001419 dependent effect Effects 0.000 claims description 14
- 230000005540 biological transmission Effects 0.000 claims description 12
- 230000007423 decrease Effects 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000007850 fluorescent dye Substances 0.000 claims description 8
- 238000000695 excitation spectrum Methods 0.000 claims description 7
- 238000002835 absorbance Methods 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 description 36
- 239000000835 fiber Substances 0.000 description 21
- 230000005284 excitation Effects 0.000 description 10
- 230000005855 radiation Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000000295 emission spectrum Methods 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 229920006240 drawn fiber Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- -1 for example Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 238000003847 radiation curing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- OUEIPKXVZRHNIB-UHFFFAOYSA-N 1-(3-pyren-1-ylpropyl)pyrene Chemical compound C1=C2C(CCCC=3C4=CC=C5C=CC=C6C=CC(C4=C65)=CC=3)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 OUEIPKXVZRHNIB-UHFFFAOYSA-N 0.000 description 1
- FCNCGHJSNVOIKE-UHFFFAOYSA-N 9,10-diphenylanthracene Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 FCNCGHJSNVOIKE-UHFFFAOYSA-N 0.000 description 1
- 206010073306 Exposure to radiation Diseases 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007586 pull-out test Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012549 training Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/123—Ultra-violet light
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/12—General methods of coating; Devices therefor
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/44—Mechanical structures for providing tensile strength and external protection for fibres, e.g. optical transmission cables
- G02B6/4479—Manufacturing methods of optical cables
- G02B6/448—Ribbon cables
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0827—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
- B29C2037/90—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/0288—Controlling heating or curing of polymers during moulding, e.g. by measuring temperatures or properties of the polymer and regulating the process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/10—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation for articles of indefinite length
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2011/00—Optical elements, e.g. lenses, prisms
- B29L2011/0075—Light guides, optical cables
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/248—Measuring crosslinking reactions
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/84—Systems specially adapted for particular applications
- G01N21/88—Investigating the presence of flaws or contamination
- G01N21/95—Investigating the presence of flaws or contamination characterised by the material or shape of the object to be examined
- G01N21/952—Inspecting the exterior surface of cylindrical bodies or wires
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T436/00—Chemistry: analytical and immunological testing
- Y10T436/13—Tracers or tags
Abstract
An article such as a drawn optical fiber (21) or an array of optical fibers is provided with a curable coating material. The array of optical fibers may be held together with a curable matrix material (45).
Included in the coating material or the matrix material is a fluorescent constituent the fluorescence emission of which changes as a function of the degree of cure of the coating or matrix material. After the in-line curing of the coating material or of the matrix material, the fluorescence emission of the fluorescent constituent is monitored to determine the degree of cure of the curable material.
Included in the coating material or the matrix material is a fluorescent constituent the fluorescence emission of which changes as a function of the degree of cure of the coating or matrix material. After the in-line curing of the coating material or of the matrix material, the fluorescence emission of the fluorescent constituent is monitored to determine the degree of cure of the curable material.
Description
- l - 20~63 ARTICLE COATED WITH CURED MATERL~L
AND METHODS OF FOR MAKING
Technical Field This invention relates to an article coated with a cured material 5 and to methods of making.
Back~round of the Invention Optical fiber may be assembled into units and provided with a sheathing systeM. Or a plurality of optical fibers may be assembled into a planar array and secured in place by a curable matrix material such as is 10 disclosed in U.S. patent 4,900,12~. This last described product is referred to as a bonded ribbon.
In both the process for coating the optical flber after it is drawn, which may include the application of primary and secondary curable coating materials, and in the process for embedding an array of optical fibers in a 15 cured matrix material, it becomes important to be able to determine the degree of cure of the curable coating or matrix material.
Suitable curing of the optical fiber coating and of the ribbon matrix material is very important. An improperly cured bonded ribbon matrix or optical fiber coating material will inhibit cabling. Also an 20 undercured coating or matrix material generally will emit an undesirable odor. Further, improperly cured coating and matrix materials exhibit poor strippability, poor adhesion and poor reliability relative to a properly cured coating and matrix material. As should be evident, properly cured coating and matrix materials for drawn optical fibers and for optical fiber ribbons 25 are important to the quality of the final product. Further, the modulus of the cured of material is a function of the degree of cure. Modulus is important to the mechanical and optical performance of the optical fiber and fiber ribbon.
Presently, there are several methods which are used to determine 30 the degree of cure of optical fiber coating materials. In one method, which is referred to as in-situ modulus test, a cut is made through the coating or coating layers to the glass. A load is applied to the optical fiber and measurements are taken as to the time during which the load is applied to the fiber and the distance through which the optical fiber moves. From 35 these measurements, the modulus of the primary coating can be determined. ~L
, In a pull-out test, a length of optical fiber is positioned in a well known Instron apparatus. The force which is necessary to pull the optical fiber from the primary coating material is measured. This measurement is proportional to the degree of cure. In a third method which is referred to as 5 the cut-through method, a length of coated optical fiber is placed into a fixture which prevents rolling of the fiber. A knife probe is caused to engage the fiber and that temperature at which the knife edge probe penetrates the coating material is measured. The greater the measured temperature, the greater the degree of cure.
There are several problems with respect to the use of the foregoing methods. First, each requires the use of relatively expensive equipment. Secondly, each is a so-called off-line test and hence is most likely not performed on 100 percent of the product throughput. Thirdly, a high level of employee training is required and lastly, the tests are operator 15 sensitive.
Needless to say, it is most desirable that in-line testing for the degree of cure be accomplished as the optical fiber or optical fiber ribbon is being moved along a path of travel to a takeup. Bonded ribbon production line speeds may be in the range of about 200 feet per minute. If an off-line 20 test were used to determine the degree of cure and hence the modulus, and if that test were to consume about five minutes, then it can be seen that about 12000 feet of optical fiber, assuming a twelve fiber ribbon, may be wasted if the degree of cure is not sufficient.
The problem of determining the degree of cure of a curable 25 coating material exists in industries other than that for optical fiber manufacture. For example, curable materials are used in the manufacture of floor tiles, furniture, medica! syringes, compact discs, computer floppy discs, video and audio tapes and glass fiber composites for automobiles and other products.
What is needed and what is not provided by the prior art are methods of monitoring the degree of cure of curable coating materials.
What is especially sought after are methods of determining the degree of cure of curable coating and matrix materials which are used to provide optical fiber transmission media. Desirably, the sought after products and 35 methods and apparatus for m~king same should be capable of being performed as the optical fiber or as the optical fiber ribbon is being moved ~ -3- 20 ~ 2263 along a m~mlf~Gtllring line.
Summag of the Invention The foregoing problems of the prior art have been overcome with the article of this invention which may be an elonE~ted strand m~t~ri~l and with the methods for making 5 same. In one ~lefe.~d embodiment the invention is directed to an optical tr~n~mi~ion medium, which compri~Ps an optical fiber tr~n~mi~sion medium, and a material system which encloses substantially said tr~n~mi~cion medium, said m~t~ri~l system compri~ing an ultraviolet light curable m~teri~l which has been cured and which has an absorbance that depends on the degree of cure of said curable m~t~ri~l and a probe comprising a material 10 which emits non-polarized light subsequent to being promoted to an excited electronic state by non-polarized light, the m~t~ri~l system being such that its emission of light spans a range dependent upon the degree of cure of said curable m~tPri~ ther, the degree of overlap of the excitation spectra of said probe and said curable material being a function of the behaviour of the absorbance of the curable material as the degree of cure changes.
lS In the m~nllf~r,tllte of optical fiber, for example, optical fiber is advanced aIong a path of travel and a curable coating m~teti~l is applied thereto. The coating m~t~ri~l which is applied to the optical fiber includes a fluolescellt con~ ent which is such that its fluorescense emission changes as a function of the degree of cure of the coating m~trri~l Then the coating material is cured and, in-line, the fluorescence emission of the 20 fluo,escellt consliluelll is monitored to determine the degree of cure of the coating m~trri~l The optical fiber having the cured coating m~teri~l is taken up. Instead of an optical fiber, the methods of this invention may be used to c~etermine the degree of cure of a matrix m~teri~l which is used to hold together a plurality of optical fibers which are dlsposed in a planar array. In either case, the in-line mom,lolillg allows steps to be taken 25 to adjust the degree of cure to that value desired.
An a~l~al~l ls for m~king an optical fiber which includes a curable coating m~t~ri~l or bonded optical fiber ribbon which includes a curable matrix m~t~ri~l includes a m~nllf~ctllring line for advancing an optical fiber coated with a W curable material or a plurality of optical fibers which have been gathered together and embedded in a W
30 curable matrix material past a source of W radiation energy. Ar~c.w~rds, the coated optical fiber or the bonded ribbon is advanced past a detector which 1~- B
~ - 20~2263 is effective to measure the degree of cure. As should be realized, the degree of cure is related to the modulus of the coating or of the matrix material.
Should the degree of cure and hence the modulus not be as desired, the detector may be used to alert an operator who makes appropriate changes 5 to obtain the desired degree of cure. The coated optical rlber or the bonded ribbon is then taken up on a spool.
Brief De~cription of the Drawin~
FIG. 1 is a schematic view of a manufacturing line which is used to provide one or multiple coating materials for a drawn optical f!ber;
FIG. 2 is an end view in section of an optical fiber having a coating provided by portions of the apparatus of F~G. l;
FIG. 3 is a schematic view of a manufacturing line which is used to provide a matrix material for a plurality of optical fibers disposed in an array;
FIG. 4 is an end view in section of an optical fiber array which is embedded in a matrix material;
FIG. 5 is a cross sectional view an elliptical reflector which is used to cure the optical fiber coating or matrix materials;
FIG. 6 depicts the modulus of a curable coating or matrix 20 material as plotted against radiation cure dose;
FIG. 7 is a graph which depicts the relationship of viscosity of a curable coating or matrix material to a W dose which is used to cure the coating or matrix material;
FIGS. 8, 9 and 10 are graphs which show relative fluorescence 25 emission of fluorescent materials versus relative viscosity of coating or matrix material in percent of full cure;
FIGS. 11 is a graph which shows absorption spectra for a coating or matrix material and for a probe and an emission spectrum for the probe;
FIG. 12 is another graph which shows an absorption spectra for a 30 coating or matrix material and for a probe and an emission spectrum for the probe;
FIGS. 13 and 14 show, respectively, relative coating or matrix material absorption versus radiation dose, and relative absorption versus wavelength as a function of cure for a material the absorption of which 35 increases as a function of the degree of cure; and FIGS. 15 and 16 show, respectively, relative coating or matrix material absorption versus radiation dose, and relative absorption versus wavelength as a function of cure for a material the absorption of which decreases as a function of the degree of cure.
5 Detailed Description Referring now to FIG. 1, there is shown an apparatus which is designated generally by the numeral ?O and in which is used to draw optical fiber 21 from a specially prepared cylindrical preform ')2 and for then coating the fiber. The optical fiber "1 is formed by locally and 10 symmetrically heating the preform '>2, typically 7 to 5 mm in diameter and 60 cm in length, to a temperature of about 2000 C. As the preform is fed into and through a furnace 23, fiber 21 is drawn from the molten material.
As can be seen in FIG. 1, the elements of the draw system include the furnace 23 wherein the preform is drawn down to the fiber size 15 after which the fiber 21 is pulled from the heat zone. The diameter of the fiber '>1 is measured by a device 24 at a point shortly after the fiber is formed and this measured value becomes an input into a control system.
Within the control system, the measured diameter is compared to the desired value and an output signal is generated to adjust the draw speed 20 such that the fiber diameter approaches the desired value.
After the diameter of the fiber 21 is measured, a protective coating 25 (see also FIG. 2) is applied to it by apparatus 27. Preservation of flber strength requires the application of the protective coating, which shields newly drawn fiber from the deleterious effects of the atmosphere.
25 This coating must be applied in a manner that does not damage the surface of the fiber 21 and such that the fiber has a predetermined diameter and is protected from abrasion during subsequent manufacturing operations, installation and service. Minimi7.ing attenuation requires the selection of a suitable coating material and a controlled application of it to the fiber. Such 30 a coating apparatus may be one such as that described in U.S. Patent 4,474,830 which issued on October 2, 1984 in the name of C. R. Taylor.
Minimizing diameter variation which in turn minimi7es the losses due to misalignment at connector and splice points requires careful design of the draw system and the continuous monitoring and control of the fiber 35 diameter duling the drawing and the coating steps of the process. Then, the coated f~lber ~1 is passed through a centering gauge 28.
Z01 ~;~63 After the coating material has been applied to the drawn fiber, the coating material must be cured. Accordingly, the optical f~lber having the coating material thereon is passed through a device 30 for curing the coating and a device 32 for measuring the outer diameter of the coated 5 fiber. Afterwards, it is moved through a capstan 34 and is spooled for testing and storage prior to subsequent cable operations.
Referring now to FIG. 3, there is shown a schematic view of a manufacturing line which is designated generally the numeral 40. The line 40 is capable of manufacturing a bonded ribbon 4~ (see FIG. 4). The ribbon 10 42 includes a plurality of coated optical fibers 36-3G each of which includes a core, a cladding and one or more layers 25-~5 of coating material.
As can be seen in FIG. 4, the optical f~lbers 36-36 may be disposed in a planar array. The fibers are held bonded together in that array by a matrix material 45. It is common to refer to such a structure as 15 a bonded ribbon. In a preferred embodiment, the matrix material is an ultraviolet (W) curable material.
Along the line 40, a plurality of the optical fibers 36-36 are payed out from supplies 46-46, and an ink from a reservoir is applied thereto by an applicator 48. Afterwards, the ink is dried in an oven 49. Then the optical 20 fibers are gathered together and embedded in the curable matrix material in an applicator 52. The applicator 52 may be an extruder, for example.
Afterwards, the array in the matrix material is directed past an apparatus 54 which is well known and which is used to cure the curable matrix material and taken up on a spool 56.
As mentioned, after the curable coating material has been applied to the drawn optical fiber or the curable matrix material to the array of optical fibers, the coating or the matrix material must be cured.
The curing of the bonded ribbon, for example, may be accomplished within apparatus which includes an elliptical reflector 60 (see FIG. 5). In it a lamp 61 is positioned at one of two focal points 63 and 65 and the article at the other. The lamp 61 is such that it emits energy at wavelengths which are suitable to cure the curable material.
The modulus of the cured coating material is dependent on the U.V. curing dose (see FIG. 6). In order to cause the modulus of the coating 35 material or the matrix material 45 of the bonded ribbon to be a desired value, the degree of cure is monitored. Although reference hereinafter may ~ 20~2263 be made only to the coating material or to the matrix material, it should be understood that the following applies to both. The methods of this invention facilitate the in-line monitoring of the degree of cure. This is accomplished by including a probe in the coating material or in the matrix 5 material. The probe comprises a material which emits light subsequent to being promoted to an excited electronic state.
In the apparatus 20, an in-line cure detector system 57 is included after the curing apparatus 30 whereas in the apparatus 40, an in-line detector system 59 precedes the spool 56. Broadly, the in-line cure 10 detector system includes a light source which emits appropriate wavelengths necessary to promote the probe to an excited electronic state and a detector which is capable of quantitatively measuring the intensity of emission from the probe as it transitions from the excited electronic state to an unexcited electronic state.
The curable matrix material, for example, is a material system which comprises a composition comprising an ultraviolet (W) curable material such as an acrylate and a probe such as, for example, a fluorescent constituent. Hereinafter, the description is couched in terms of a W curable coating or matrix material and a fluorescent probe. The system is such that 20 its emission of light changes as a function of the degree of cure of the curable material. Emission from the fluorescent material provides a signature or a fingerprint of the probe constituent in the material. This signature or fingerprint remains with the curable material after the curable material has been cured and provides about the same emission level 25 thereafter.
The unique excitation and emission spectra of a material system functions as the signature or fingerprint for the curable material system or for the final product subsequent to manufaeture. After the W absorption spectrum of the material system or of the article containing the cured 30 system has been determined, excitation at the longest wavelength of the W
absorption spectrum will yield a fluorescence emission spectrum.
Subsequently, determination of the characteristic fluorescence excitation spectrum for the wavelength corresponding to the maximum fluorescence emission will yield the excitation spectrum of the fluoreseent probe. The 35 very fact that an emission spectrum results upon excitation of the curable material system or of the article containing the cured material system is ~ 2012Z63 indicative of the use of a curable material system which includes a constituent probe.
The enclosing material system of the optical fiber or of the fiber array must be one such that under cure, the fluorescence emission of the 5 material system changes with the degree of cure. The fluorescent probe constituent is such that its fluorescence emission is dependent on the degree of cure of the coating or matrix material.
Properties of the fluorescent matelial may change because of the change in the polymer coating material which changes the fluorescence 10 emission of the probe. There are several ways in which the fluorescence emission may change and these are best seen by relating that change to viscosity of the coating or matrix material being cured.
The probe is an organic material that has a fluorescent form that may be dependent on its orientation in space. That orientation is 15 dependent on its mobility which changes with the degree of cure of the optical fiber coating or matrix material. As the coating or matrix material cures, its viscosity increases (see FIG.7) until it becomes a solid. At that time, there is no further increase in viscosity and further change in fluorescence emission does not occur.
For those probe materials in which the fluorescence emission is dependent on orientation in space, the emission may increase as a function of viscosity (see FIG.8) or it may decrease (see FIG.9). Further, the curable coating or matrix system may include a fluorescent constituent which is such that it is independent of the viscosity (see FIG.10), however, 25 in that type the fluorescence emission of the system is such that it changes as a function of the absorption of the coating or matrix material which is dependent on the degree of cure of the coating or matrix material.
If as the enclosing coating or matrix material is cured and its viscosity increases, the orientation of the probe favors increased 30 fluorescence, then the intensity of emission increases as a function of the degree of cure (see again FIG. 8). During cure of the optical fiber coating or matrix material, the motion of the fluorescent probe is restricted to favor the fluorescent form. A system which includes a coating or matrix material and this kind of probe may be referred to as a Type A system. On the 35 other hand, if as the enclosing coating or matrix material is cured and viscosity increases, the orientation favors less fluorescence, then the ~_~ 20~ 63 intensity of emission decreases as a function of cure (see again FIG. ~). A
system which includes a coating or a matrix material and this latter kind of probe is referred to herein as a Type B system.
For the foregoing two approaches, i.e. types A and B, the 5 absorption wavelength of the fluorescent probe must exceed substantially that of the matrix material. Any overlap of the absorption of the coating or matrix material with the absorption of the probe must be insubstantial.
Viewing now FIG. 11, there is shown a graph which depicts absorption of the coating or matrix material and of the probe and fluorescence emission 10 of the probe plotted as a function of wavelength. As can be seen, the wavelength at which the fluorescence emission of the probe is a maximum is displaced from that at which the absorption of the probe reaches a maximum value. This displacement of the emission wavelength from the absorption wavelength is well known and is referred to as the Stokes shift.
15 If this condition be satisfied as in FIG. 11, then any change in the probe emission is due to a change of its orientation in space and hence of its fluorescence as a function of the degree of cure. This arrangement is effective because as the coating or matrix material transitions from a liquid to a solid material, its viscosity increases from about 10000 cps at 23 C to 20 a solid. The more viscous the matrix material, the less mobile is the probe material. As the degree of cure increases, the relative intensity of the emission of the probe increases or decreases, unaffected by the absorption or emission of the coating or of the matrix material.
A third approach is to use a fluorescent probe constituent which 25 is independent of the viscosity of the coating or matrix material during cure (see again FIG. 10). A system which includes a coating material and such a probe is referred to herein as a Type C system. Such a system is ideal when the absorption characteristic of the probe is substantially the same as that of the coating or matrix material. If the fluorescence of the 30 probe remains the same as a function of the viscosity of the medium which is dependent on the degree of cure, then reliance must be put on the properties of the coating or matrix material. The transmission of the coating or matrix material changes as a function of the degree of cure.
For a Type C system to be a viable one, there are three 35 requirements. First, it must be known that the emission inlensity of the probe is not dependent on its orientation in space which is dependent on Z0~2263 ~ . . ~.
the viscosity of the coating or matrix material. That is, the fluorescence is independent of the viscosity of the medium. Secondly, it must be known that the excitation spectrum of the probe is coincident with or has somewhat substantial overlap with the absorption spectrum of the curable 5 matrix or coating material (see FIG. 1~). Thirdly, the coating or matrix material must have an absorption which is cure dependent.
For some W coating and matrix materials, percent relative absorption of W r adiation increases with respect to the radiation curing dose. For example, viewing FIG. 13, it is seen that a curve 70 increases until 10 it plateaus at about 80% absorption at a given wavelength. Viewing now FIG. 14, there is shown a family of curves 72, 73, 74 and 76 with the relative absorption in percent being the ordinate and the wavelength of radiation being the abscissa. The curve 7~ of FIG. 14 represents a coating or matrix material in liquid form. For curve 73, the cure dose is 0.13 Joule/cm2, for 15 curve 74, 0.')5 Joule/cm2 and for curve 76, 0.5 Joule/cm2. These curves illustrate that for some materials, the W absorption increases with the degree of cure.
For other W coating and matrix materials, the absorption decreases as a function of the degree of cure. Curves exemplary of these 20 kinds of materials are shown in FIGS. 15 and 16. As is seen by a curve 80 in FIG. 15, the relative absorption in percent of a matrix or coating material decreases with increasing radiation curing dose as expressed in Joules per square centimeter. In FIG. 16, a family of curves 8~, ~3. 84 and 86 represent plots of the relative absorption in percent versus wavelength. The curve 82 25 represents a liquid as applied as a coating or as a malrix material. As is seen, as the coating or the matrix materials represented by this family of curves undergo an increasing cure dose of radiation energy, the percent absorption decreases. The curve 83 represents a plot of percent absorption versus wavelength for a cure dose of 0.13 Joule/cm2, curve 84 for 0.25 30 Joule/cm2 and curve 86 for 0.5 Joule/cm2.
Transmission and absorption are inversely related. If the above-mentioned three mentioned requirements for a Type C system be met and a coating or matrix material as characterized by the graphs of FIGS. 13 and 14 be used, then upon excitation, as the matrix material absorbs more 35 radiation as a function of cure, there is less light which reaches the probe constituent and hence there is less fluorescence emission. The greater the ~ - 2012263 cure of the matrix material, the more its absorption increases. In effect, the arrangement uses the attenuation of light reaching the probe to excite it.
Conversely, if a coating or matrix material characterized by the graphs of FIGS. 15 and 16 be used, then upon excitation, as the coating or matrix 5 material absorbs less radiation as a function of cure, more light reaches the probe constituent and hence there is more fluorescence emission.
A Type C system is operative independent of the viscosity of the coating or matrix material whereas type A or B includes a viscosity dependent probe. Instead, in a Type C system, reliance is placed on the 10 absorption of the coating or matrix material to attenuate the light which excites the probe. In using the probe characterized by FIG. 10, the fluorescence of the coating or matrix system does not depend on the mobility of the probe, but rather on the light absorption of the coating or matrix material. In this kind of coating system, the absorption of the 15 coating or matrix material changes as it cures. This is not desirable in the types shown in FIGS. 8 and 9, for there, a fluorescent probe, the absorption of which is different from that of the matrix, is chosen.
In none of the three techniques described hereinabove does the fluorescent material cure. Rather it is trapped in the matrix or in the 20 optical fiber coating material. In Type A and B systems, the probe mobility becomes restricted as the viscosity of the coating or matrix material increases and the fluorescence changes. In a Type C system, reliance is placed on the absorption of the coating or matrix material because the probe has a fluorescence emission which is viscosity independent. Further, 25 the fluorescence emission of the material system is substantially constant over time, and, following cure of the curable coating or matrix material, functions as a fingerprint for the system at anytime thereafter.
There are other kinds of probes which may be used. If a probe is consumed by, for example, a photoreaction, less absorption may occur. One 30 of these other kinds of probes is characterized in that it reacts with itself, whereas another is characterized in that it undergoes a photoreaction with components of the coating or with components of the matrix material. As the material is exposed to radiation, the absorption is decreased because it is consumed by reacting with itself or with the coating or matrix material.
35 It becomes ;mportant to choose a probe constituent that on exposure to radiation does not become non-fluorescent and one such that the absorption ~ - 1"- 20 1 2263 of the probe constituent does not change with respect to the degree of cure of the coating or matrix material. Desirably, a probe is selected the emission of which increases or decreases. If the probe is consumed by or reacts with the coating or the rnatri~ material, the absorption of the probe decreases 5 and there occurs a decrease in the em;ssion of the material.
Systems designated types A, B and C are preferred. For a probe reaction with itself in the concentrations used herein, i.e. ppm, the probal)ility of reacting tlIe probe with itself ;s low. If the concentration of the probe material is increased, the coat;ng or matri~ material is perturbed 10 whicl1 affects the properties such as aging and cure speed of the material.
As the material cures, viscosity increases which increases the difficulty for one molecule of the probe material to reach another. These other kinds of probes just described are not preferred because of the concentration levels present and because the mobility of the probes is decreased as a result of 15 increasing viscosity during cure.
It should be understood that although the preferred embodiment has been described as an article comprising an optical fiber provided with a curable coating system or an array of optical fibers provided with a curable matrix material, that the invention has many other uses. It may be used to 20 monitor the degree of cure of curable materials used to manufacture floor tile, furniture, syringes for medical use, compact audio discs, computer floppy discs, video and audio tapes and glass fiber composites for automob;les and other products.
~ Tlle invention has been described i~ terms of adding a probe to a 25 coating or matri~; material to provide a material system. It should be understood that the coating or matri~; material having a component the emission of light from which is dependent upon the degree of cure may be used.
E~cample 1 One half gram of a solution comprising 0.05 gram 1,3-bispyrenylpropane ;n "5 ml. N-vinylpyrrolidone was blended with 100 grams of Cabelite 3287-9-11, a W curable acrylate-based material commercially available from DeSoto, Inc., Des Plaines, Illinois. The resulting material system was of Type B. Irradiation of this formulation on release paper with a W dose of 0.~5 Joule/cm'' provided a 0.05 mm film with a 395 nm fluorescence of 73~o on a scale of 0 to 100, i.e. 73~ of full scale. The * trade mark ~.
instrument 0% reading was set with no sample in the instrument upon excitation at 350 nm. Irradiation of this formulation on release paper with a W dose of 0.5 J/cm2 provided a 0.05 mm film with a 395 nm fluorescence of 49~o upon excitation at 350 nm. Irradiation of this formulation at 1.0 5 J/cm2 provided a 0.05 mm film with a 395 nm fluorescence of 13~o full scale upon excitation at 350 nm.
Example 2 One half gram of a solution comprising 0.125 gram 9,10-diphenylanthracene in 25 ml. N-villylpyrrolidone was blended with 100 10 grams of Cabelite 3~87-9-11, a UV curable material commercially available from DeSoto, Inc., Des Plaines, Illinois. The resulting material system relied on changes in the absorption of the W constituent to effect changes in fluorescence emission of the probe. As such, this is an example of a Type C
material system. Irradiation of this formulation on release paper with a W
15 dose of 0.25 Joule/ cm2 provided a 0.05 mm film with 430 nm fluorescence of 57% upon excitation at 380 nm. Irradiation of this formulation on release paper with a W dose of 1.0 Joule/ cm2 provided a 0.05 mm film with a 430 nm fluorescence of 25% upon excitation at 380 nm.
It is to be understood that the above-described arrangements are 20 simply illustrative of the invention. Other arrangements may be devised by those skilled in the art which will embody the principles of the invention and fall within the spirit and scope thereof.
AND METHODS OF FOR MAKING
Technical Field This invention relates to an article coated with a cured material 5 and to methods of making.
Back~round of the Invention Optical fiber may be assembled into units and provided with a sheathing systeM. Or a plurality of optical fibers may be assembled into a planar array and secured in place by a curable matrix material such as is 10 disclosed in U.S. patent 4,900,12~. This last described product is referred to as a bonded ribbon.
In both the process for coating the optical flber after it is drawn, which may include the application of primary and secondary curable coating materials, and in the process for embedding an array of optical fibers in a 15 cured matrix material, it becomes important to be able to determine the degree of cure of the curable coating or matrix material.
Suitable curing of the optical fiber coating and of the ribbon matrix material is very important. An improperly cured bonded ribbon matrix or optical fiber coating material will inhibit cabling. Also an 20 undercured coating or matrix material generally will emit an undesirable odor. Further, improperly cured coating and matrix materials exhibit poor strippability, poor adhesion and poor reliability relative to a properly cured coating and matrix material. As should be evident, properly cured coating and matrix materials for drawn optical fibers and for optical fiber ribbons 25 are important to the quality of the final product. Further, the modulus of the cured of material is a function of the degree of cure. Modulus is important to the mechanical and optical performance of the optical fiber and fiber ribbon.
Presently, there are several methods which are used to determine 30 the degree of cure of optical fiber coating materials. In one method, which is referred to as in-situ modulus test, a cut is made through the coating or coating layers to the glass. A load is applied to the optical fiber and measurements are taken as to the time during which the load is applied to the fiber and the distance through which the optical fiber moves. From 35 these measurements, the modulus of the primary coating can be determined. ~L
, In a pull-out test, a length of optical fiber is positioned in a well known Instron apparatus. The force which is necessary to pull the optical fiber from the primary coating material is measured. This measurement is proportional to the degree of cure. In a third method which is referred to as 5 the cut-through method, a length of coated optical fiber is placed into a fixture which prevents rolling of the fiber. A knife probe is caused to engage the fiber and that temperature at which the knife edge probe penetrates the coating material is measured. The greater the measured temperature, the greater the degree of cure.
There are several problems with respect to the use of the foregoing methods. First, each requires the use of relatively expensive equipment. Secondly, each is a so-called off-line test and hence is most likely not performed on 100 percent of the product throughput. Thirdly, a high level of employee training is required and lastly, the tests are operator 15 sensitive.
Needless to say, it is most desirable that in-line testing for the degree of cure be accomplished as the optical fiber or optical fiber ribbon is being moved along a path of travel to a takeup. Bonded ribbon production line speeds may be in the range of about 200 feet per minute. If an off-line 20 test were used to determine the degree of cure and hence the modulus, and if that test were to consume about five minutes, then it can be seen that about 12000 feet of optical fiber, assuming a twelve fiber ribbon, may be wasted if the degree of cure is not sufficient.
The problem of determining the degree of cure of a curable 25 coating material exists in industries other than that for optical fiber manufacture. For example, curable materials are used in the manufacture of floor tiles, furniture, medica! syringes, compact discs, computer floppy discs, video and audio tapes and glass fiber composites for automobiles and other products.
What is needed and what is not provided by the prior art are methods of monitoring the degree of cure of curable coating materials.
What is especially sought after are methods of determining the degree of cure of curable coating and matrix materials which are used to provide optical fiber transmission media. Desirably, the sought after products and 35 methods and apparatus for m~king same should be capable of being performed as the optical fiber or as the optical fiber ribbon is being moved ~ -3- 20 ~ 2263 along a m~mlf~Gtllring line.
Summag of the Invention The foregoing problems of the prior art have been overcome with the article of this invention which may be an elonE~ted strand m~t~ri~l and with the methods for making 5 same. In one ~lefe.~d embodiment the invention is directed to an optical tr~n~mi~ion medium, which compri~Ps an optical fiber tr~n~mi~sion medium, and a material system which encloses substantially said tr~n~mi~cion medium, said m~t~ri~l system compri~ing an ultraviolet light curable m~teri~l which has been cured and which has an absorbance that depends on the degree of cure of said curable m~t~ri~l and a probe comprising a material 10 which emits non-polarized light subsequent to being promoted to an excited electronic state by non-polarized light, the m~t~ri~l system being such that its emission of light spans a range dependent upon the degree of cure of said curable m~tPri~ ther, the degree of overlap of the excitation spectra of said probe and said curable material being a function of the behaviour of the absorbance of the curable material as the degree of cure changes.
lS In the m~nllf~r,tllte of optical fiber, for example, optical fiber is advanced aIong a path of travel and a curable coating m~teti~l is applied thereto. The coating m~t~ri~l which is applied to the optical fiber includes a fluolescellt con~ ent which is such that its fluorescense emission changes as a function of the degree of cure of the coating m~trri~l Then the coating material is cured and, in-line, the fluorescence emission of the 20 fluo,escellt consliluelll is monitored to determine the degree of cure of the coating m~trri~l The optical fiber having the cured coating m~teri~l is taken up. Instead of an optical fiber, the methods of this invention may be used to c~etermine the degree of cure of a matrix m~teri~l which is used to hold together a plurality of optical fibers which are dlsposed in a planar array. In either case, the in-line mom,lolillg allows steps to be taken 25 to adjust the degree of cure to that value desired.
An a~l~al~l ls for m~king an optical fiber which includes a curable coating m~t~ri~l or bonded optical fiber ribbon which includes a curable matrix m~t~ri~l includes a m~nllf~ctllring line for advancing an optical fiber coated with a W curable material or a plurality of optical fibers which have been gathered together and embedded in a W
30 curable matrix material past a source of W radiation energy. Ar~c.w~rds, the coated optical fiber or the bonded ribbon is advanced past a detector which 1~- B
~ - 20~2263 is effective to measure the degree of cure. As should be realized, the degree of cure is related to the modulus of the coating or of the matrix material.
Should the degree of cure and hence the modulus not be as desired, the detector may be used to alert an operator who makes appropriate changes 5 to obtain the desired degree of cure. The coated optical rlber or the bonded ribbon is then taken up on a spool.
Brief De~cription of the Drawin~
FIG. 1 is a schematic view of a manufacturing line which is used to provide one or multiple coating materials for a drawn optical f!ber;
FIG. 2 is an end view in section of an optical fiber having a coating provided by portions of the apparatus of F~G. l;
FIG. 3 is a schematic view of a manufacturing line which is used to provide a matrix material for a plurality of optical fibers disposed in an array;
FIG. 4 is an end view in section of an optical fiber array which is embedded in a matrix material;
FIG. 5 is a cross sectional view an elliptical reflector which is used to cure the optical fiber coating or matrix materials;
FIG. 6 depicts the modulus of a curable coating or matrix 20 material as plotted against radiation cure dose;
FIG. 7 is a graph which depicts the relationship of viscosity of a curable coating or matrix material to a W dose which is used to cure the coating or matrix material;
FIGS. 8, 9 and 10 are graphs which show relative fluorescence 25 emission of fluorescent materials versus relative viscosity of coating or matrix material in percent of full cure;
FIGS. 11 is a graph which shows absorption spectra for a coating or matrix material and for a probe and an emission spectrum for the probe;
FIG. 12 is another graph which shows an absorption spectra for a 30 coating or matrix material and for a probe and an emission spectrum for the probe;
FIGS. 13 and 14 show, respectively, relative coating or matrix material absorption versus radiation dose, and relative absorption versus wavelength as a function of cure for a material the absorption of which 35 increases as a function of the degree of cure; and FIGS. 15 and 16 show, respectively, relative coating or matrix material absorption versus radiation dose, and relative absorption versus wavelength as a function of cure for a material the absorption of which decreases as a function of the degree of cure.
5 Detailed Description Referring now to FIG. 1, there is shown an apparatus which is designated generally by the numeral ?O and in which is used to draw optical fiber 21 from a specially prepared cylindrical preform ')2 and for then coating the fiber. The optical fiber "1 is formed by locally and 10 symmetrically heating the preform '>2, typically 7 to 5 mm in diameter and 60 cm in length, to a temperature of about 2000 C. As the preform is fed into and through a furnace 23, fiber 21 is drawn from the molten material.
As can be seen in FIG. 1, the elements of the draw system include the furnace 23 wherein the preform is drawn down to the fiber size 15 after which the fiber 21 is pulled from the heat zone. The diameter of the fiber '>1 is measured by a device 24 at a point shortly after the fiber is formed and this measured value becomes an input into a control system.
Within the control system, the measured diameter is compared to the desired value and an output signal is generated to adjust the draw speed 20 such that the fiber diameter approaches the desired value.
After the diameter of the fiber 21 is measured, a protective coating 25 (see also FIG. 2) is applied to it by apparatus 27. Preservation of flber strength requires the application of the protective coating, which shields newly drawn fiber from the deleterious effects of the atmosphere.
25 This coating must be applied in a manner that does not damage the surface of the fiber 21 and such that the fiber has a predetermined diameter and is protected from abrasion during subsequent manufacturing operations, installation and service. Minimi7.ing attenuation requires the selection of a suitable coating material and a controlled application of it to the fiber. Such 30 a coating apparatus may be one such as that described in U.S. Patent 4,474,830 which issued on October 2, 1984 in the name of C. R. Taylor.
Minimizing diameter variation which in turn minimi7es the losses due to misalignment at connector and splice points requires careful design of the draw system and the continuous monitoring and control of the fiber 35 diameter duling the drawing and the coating steps of the process. Then, the coated f~lber ~1 is passed through a centering gauge 28.
Z01 ~;~63 After the coating material has been applied to the drawn fiber, the coating material must be cured. Accordingly, the optical f~lber having the coating material thereon is passed through a device 30 for curing the coating and a device 32 for measuring the outer diameter of the coated 5 fiber. Afterwards, it is moved through a capstan 34 and is spooled for testing and storage prior to subsequent cable operations.
Referring now to FIG. 3, there is shown a schematic view of a manufacturing line which is designated generally the numeral 40. The line 40 is capable of manufacturing a bonded ribbon 4~ (see FIG. 4). The ribbon 10 42 includes a plurality of coated optical fibers 36-3G each of which includes a core, a cladding and one or more layers 25-~5 of coating material.
As can be seen in FIG. 4, the optical f~lbers 36-36 may be disposed in a planar array. The fibers are held bonded together in that array by a matrix material 45. It is common to refer to such a structure as 15 a bonded ribbon. In a preferred embodiment, the matrix material is an ultraviolet (W) curable material.
Along the line 40, a plurality of the optical fibers 36-36 are payed out from supplies 46-46, and an ink from a reservoir is applied thereto by an applicator 48. Afterwards, the ink is dried in an oven 49. Then the optical 20 fibers are gathered together and embedded in the curable matrix material in an applicator 52. The applicator 52 may be an extruder, for example.
Afterwards, the array in the matrix material is directed past an apparatus 54 which is well known and which is used to cure the curable matrix material and taken up on a spool 56.
As mentioned, after the curable coating material has been applied to the drawn optical fiber or the curable matrix material to the array of optical fibers, the coating or the matrix material must be cured.
The curing of the bonded ribbon, for example, may be accomplished within apparatus which includes an elliptical reflector 60 (see FIG. 5). In it a lamp 61 is positioned at one of two focal points 63 and 65 and the article at the other. The lamp 61 is such that it emits energy at wavelengths which are suitable to cure the curable material.
The modulus of the cured coating material is dependent on the U.V. curing dose (see FIG. 6). In order to cause the modulus of the coating 35 material or the matrix material 45 of the bonded ribbon to be a desired value, the degree of cure is monitored. Although reference hereinafter may ~ 20~2263 be made only to the coating material or to the matrix material, it should be understood that the following applies to both. The methods of this invention facilitate the in-line monitoring of the degree of cure. This is accomplished by including a probe in the coating material or in the matrix 5 material. The probe comprises a material which emits light subsequent to being promoted to an excited electronic state.
In the apparatus 20, an in-line cure detector system 57 is included after the curing apparatus 30 whereas in the apparatus 40, an in-line detector system 59 precedes the spool 56. Broadly, the in-line cure 10 detector system includes a light source which emits appropriate wavelengths necessary to promote the probe to an excited electronic state and a detector which is capable of quantitatively measuring the intensity of emission from the probe as it transitions from the excited electronic state to an unexcited electronic state.
The curable matrix material, for example, is a material system which comprises a composition comprising an ultraviolet (W) curable material such as an acrylate and a probe such as, for example, a fluorescent constituent. Hereinafter, the description is couched in terms of a W curable coating or matrix material and a fluorescent probe. The system is such that 20 its emission of light changes as a function of the degree of cure of the curable material. Emission from the fluorescent material provides a signature or a fingerprint of the probe constituent in the material. This signature or fingerprint remains with the curable material after the curable material has been cured and provides about the same emission level 25 thereafter.
The unique excitation and emission spectra of a material system functions as the signature or fingerprint for the curable material system or for the final product subsequent to manufaeture. After the W absorption spectrum of the material system or of the article containing the cured 30 system has been determined, excitation at the longest wavelength of the W
absorption spectrum will yield a fluorescence emission spectrum.
Subsequently, determination of the characteristic fluorescence excitation spectrum for the wavelength corresponding to the maximum fluorescence emission will yield the excitation spectrum of the fluoreseent probe. The 35 very fact that an emission spectrum results upon excitation of the curable material system or of the article containing the cured material system is ~ 2012Z63 indicative of the use of a curable material system which includes a constituent probe.
The enclosing material system of the optical fiber or of the fiber array must be one such that under cure, the fluorescence emission of the 5 material system changes with the degree of cure. The fluorescent probe constituent is such that its fluorescence emission is dependent on the degree of cure of the coating or matrix material.
Properties of the fluorescent matelial may change because of the change in the polymer coating material which changes the fluorescence 10 emission of the probe. There are several ways in which the fluorescence emission may change and these are best seen by relating that change to viscosity of the coating or matrix material being cured.
The probe is an organic material that has a fluorescent form that may be dependent on its orientation in space. That orientation is 15 dependent on its mobility which changes with the degree of cure of the optical fiber coating or matrix material. As the coating or matrix material cures, its viscosity increases (see FIG.7) until it becomes a solid. At that time, there is no further increase in viscosity and further change in fluorescence emission does not occur.
For those probe materials in which the fluorescence emission is dependent on orientation in space, the emission may increase as a function of viscosity (see FIG.8) or it may decrease (see FIG.9). Further, the curable coating or matrix system may include a fluorescent constituent which is such that it is independent of the viscosity (see FIG.10), however, 25 in that type the fluorescence emission of the system is such that it changes as a function of the absorption of the coating or matrix material which is dependent on the degree of cure of the coating or matrix material.
If as the enclosing coating or matrix material is cured and its viscosity increases, the orientation of the probe favors increased 30 fluorescence, then the intensity of emission increases as a function of the degree of cure (see again FIG. 8). During cure of the optical fiber coating or matrix material, the motion of the fluorescent probe is restricted to favor the fluorescent form. A system which includes a coating or matrix material and this kind of probe may be referred to as a Type A system. On the 35 other hand, if as the enclosing coating or matrix material is cured and viscosity increases, the orientation favors less fluorescence, then the ~_~ 20~ 63 intensity of emission decreases as a function of cure (see again FIG. ~). A
system which includes a coating or a matrix material and this latter kind of probe is referred to herein as a Type B system.
For the foregoing two approaches, i.e. types A and B, the 5 absorption wavelength of the fluorescent probe must exceed substantially that of the matrix material. Any overlap of the absorption of the coating or matrix material with the absorption of the probe must be insubstantial.
Viewing now FIG. 11, there is shown a graph which depicts absorption of the coating or matrix material and of the probe and fluorescence emission 10 of the probe plotted as a function of wavelength. As can be seen, the wavelength at which the fluorescence emission of the probe is a maximum is displaced from that at which the absorption of the probe reaches a maximum value. This displacement of the emission wavelength from the absorption wavelength is well known and is referred to as the Stokes shift.
15 If this condition be satisfied as in FIG. 11, then any change in the probe emission is due to a change of its orientation in space and hence of its fluorescence as a function of the degree of cure. This arrangement is effective because as the coating or matrix material transitions from a liquid to a solid material, its viscosity increases from about 10000 cps at 23 C to 20 a solid. The more viscous the matrix material, the less mobile is the probe material. As the degree of cure increases, the relative intensity of the emission of the probe increases or decreases, unaffected by the absorption or emission of the coating or of the matrix material.
A third approach is to use a fluorescent probe constituent which 25 is independent of the viscosity of the coating or matrix material during cure (see again FIG. 10). A system which includes a coating material and such a probe is referred to herein as a Type C system. Such a system is ideal when the absorption characteristic of the probe is substantially the same as that of the coating or matrix material. If the fluorescence of the 30 probe remains the same as a function of the viscosity of the medium which is dependent on the degree of cure, then reliance must be put on the properties of the coating or matrix material. The transmission of the coating or matrix material changes as a function of the degree of cure.
For a Type C system to be a viable one, there are three 35 requirements. First, it must be known that the emission inlensity of the probe is not dependent on its orientation in space which is dependent on Z0~2263 ~ . . ~.
the viscosity of the coating or matrix material. That is, the fluorescence is independent of the viscosity of the medium. Secondly, it must be known that the excitation spectrum of the probe is coincident with or has somewhat substantial overlap with the absorption spectrum of the curable 5 matrix or coating material (see FIG. 1~). Thirdly, the coating or matrix material must have an absorption which is cure dependent.
For some W coating and matrix materials, percent relative absorption of W r adiation increases with respect to the radiation curing dose. For example, viewing FIG. 13, it is seen that a curve 70 increases until 10 it plateaus at about 80% absorption at a given wavelength. Viewing now FIG. 14, there is shown a family of curves 72, 73, 74 and 76 with the relative absorption in percent being the ordinate and the wavelength of radiation being the abscissa. The curve 7~ of FIG. 14 represents a coating or matrix material in liquid form. For curve 73, the cure dose is 0.13 Joule/cm2, for 15 curve 74, 0.')5 Joule/cm2 and for curve 76, 0.5 Joule/cm2. These curves illustrate that for some materials, the W absorption increases with the degree of cure.
For other W coating and matrix materials, the absorption decreases as a function of the degree of cure. Curves exemplary of these 20 kinds of materials are shown in FIGS. 15 and 16. As is seen by a curve 80 in FIG. 15, the relative absorption in percent of a matrix or coating material decreases with increasing radiation curing dose as expressed in Joules per square centimeter. In FIG. 16, a family of curves 8~, ~3. 84 and 86 represent plots of the relative absorption in percent versus wavelength. The curve 82 25 represents a liquid as applied as a coating or as a malrix material. As is seen, as the coating or the matrix materials represented by this family of curves undergo an increasing cure dose of radiation energy, the percent absorption decreases. The curve 83 represents a plot of percent absorption versus wavelength for a cure dose of 0.13 Joule/cm2, curve 84 for 0.25 30 Joule/cm2 and curve 86 for 0.5 Joule/cm2.
Transmission and absorption are inversely related. If the above-mentioned three mentioned requirements for a Type C system be met and a coating or matrix material as characterized by the graphs of FIGS. 13 and 14 be used, then upon excitation, as the matrix material absorbs more 35 radiation as a function of cure, there is less light which reaches the probe constituent and hence there is less fluorescence emission. The greater the ~ - 2012263 cure of the matrix material, the more its absorption increases. In effect, the arrangement uses the attenuation of light reaching the probe to excite it.
Conversely, if a coating or matrix material characterized by the graphs of FIGS. 15 and 16 be used, then upon excitation, as the coating or matrix 5 material absorbs less radiation as a function of cure, more light reaches the probe constituent and hence there is more fluorescence emission.
A Type C system is operative independent of the viscosity of the coating or matrix material whereas type A or B includes a viscosity dependent probe. Instead, in a Type C system, reliance is placed on the 10 absorption of the coating or matrix material to attenuate the light which excites the probe. In using the probe characterized by FIG. 10, the fluorescence of the coating or matrix system does not depend on the mobility of the probe, but rather on the light absorption of the coating or matrix material. In this kind of coating system, the absorption of the 15 coating or matrix material changes as it cures. This is not desirable in the types shown in FIGS. 8 and 9, for there, a fluorescent probe, the absorption of which is different from that of the matrix, is chosen.
In none of the three techniques described hereinabove does the fluorescent material cure. Rather it is trapped in the matrix or in the 20 optical fiber coating material. In Type A and B systems, the probe mobility becomes restricted as the viscosity of the coating or matrix material increases and the fluorescence changes. In a Type C system, reliance is placed on the absorption of the coating or matrix material because the probe has a fluorescence emission which is viscosity independent. Further, 25 the fluorescence emission of the material system is substantially constant over time, and, following cure of the curable coating or matrix material, functions as a fingerprint for the system at anytime thereafter.
There are other kinds of probes which may be used. If a probe is consumed by, for example, a photoreaction, less absorption may occur. One 30 of these other kinds of probes is characterized in that it reacts with itself, whereas another is characterized in that it undergoes a photoreaction with components of the coating or with components of the matrix material. As the material is exposed to radiation, the absorption is decreased because it is consumed by reacting with itself or with the coating or matrix material.
35 It becomes ;mportant to choose a probe constituent that on exposure to radiation does not become non-fluorescent and one such that the absorption ~ - 1"- 20 1 2263 of the probe constituent does not change with respect to the degree of cure of the coating or matrix material. Desirably, a probe is selected the emission of which increases or decreases. If the probe is consumed by or reacts with the coating or the rnatri~ material, the absorption of the probe decreases 5 and there occurs a decrease in the em;ssion of the material.
Systems designated types A, B and C are preferred. For a probe reaction with itself in the concentrations used herein, i.e. ppm, the probal)ility of reacting tlIe probe with itself ;s low. If the concentration of the probe material is increased, the coat;ng or matri~ material is perturbed 10 whicl1 affects the properties such as aging and cure speed of the material.
As the material cures, viscosity increases which increases the difficulty for one molecule of the probe material to reach another. These other kinds of probes just described are not preferred because of the concentration levels present and because the mobility of the probes is decreased as a result of 15 increasing viscosity during cure.
It should be understood that although the preferred embodiment has been described as an article comprising an optical fiber provided with a curable coating system or an array of optical fibers provided with a curable matrix material, that the invention has many other uses. It may be used to 20 monitor the degree of cure of curable materials used to manufacture floor tile, furniture, syringes for medical use, compact audio discs, computer floppy discs, video and audio tapes and glass fiber composites for automob;les and other products.
~ Tlle invention has been described i~ terms of adding a probe to a 25 coating or matri~; material to provide a material system. It should be understood that the coating or matri~; material having a component the emission of light from which is dependent upon the degree of cure may be used.
E~cample 1 One half gram of a solution comprising 0.05 gram 1,3-bispyrenylpropane ;n "5 ml. N-vinylpyrrolidone was blended with 100 grams of Cabelite 3287-9-11, a W curable acrylate-based material commercially available from DeSoto, Inc., Des Plaines, Illinois. The resulting material system was of Type B. Irradiation of this formulation on release paper with a W dose of 0.~5 Joule/cm'' provided a 0.05 mm film with a 395 nm fluorescence of 73~o on a scale of 0 to 100, i.e. 73~ of full scale. The * trade mark ~.
instrument 0% reading was set with no sample in the instrument upon excitation at 350 nm. Irradiation of this formulation on release paper with a W dose of 0.5 J/cm2 provided a 0.05 mm film with a 395 nm fluorescence of 49~o upon excitation at 350 nm. Irradiation of this formulation at 1.0 5 J/cm2 provided a 0.05 mm film with a 395 nm fluorescence of 13~o full scale upon excitation at 350 nm.
Example 2 One half gram of a solution comprising 0.125 gram 9,10-diphenylanthracene in 25 ml. N-villylpyrrolidone was blended with 100 10 grams of Cabelite 3~87-9-11, a UV curable material commercially available from DeSoto, Inc., Des Plaines, Illinois. The resulting material system relied on changes in the absorption of the W constituent to effect changes in fluorescence emission of the probe. As such, this is an example of a Type C
material system. Irradiation of this formulation on release paper with a W
15 dose of 0.25 Joule/ cm2 provided a 0.05 mm film with 430 nm fluorescence of 57% upon excitation at 380 nm. Irradiation of this formulation on release paper with a W dose of 1.0 Joule/ cm2 provided a 0.05 mm film with a 430 nm fluorescence of 25% upon excitation at 380 nm.
It is to be understood that the above-described arrangements are 20 simply illustrative of the invention. Other arrangements may be devised by those skilled in the art which will embody the principles of the invention and fall within the spirit and scope thereof.
Claims (12)
1. An optical transmission medium, which comprises:
an optical fiber transmission medium; and a material system which encloses substantially said transmission medium, said mateiral system comprising an ultraviolet light curable material which has been cured and which has an absorbance that depends on the degree of cure of said curable material and a probe comprising a material which emits non-polarized light subsequent to being promoted to an excited electronic state by non-polarized light, the material system being such that its emission of light spans a range dependent upon the degree of cure of said curable material, further, the degree of overlap of the excitation spectra of said probe and said curable material being a function of the behaviour of the absorbance of the curable material as the degree of cure changes.
an optical fiber transmission medium; and a material system which encloses substantially said transmission medium, said mateiral system comprising an ultraviolet light curable material which has been cured and which has an absorbance that depends on the degree of cure of said curable material and a probe comprising a material which emits non-polarized light subsequent to being promoted to an excited electronic state by non-polarized light, the material system being such that its emission of light spans a range dependent upon the degree of cure of said curable material, further, the degree of overlap of the excitation spectra of said probe and said curable material being a function of the behaviour of the absorbance of the curable material as the degree of cure changes.
2. The optical transmission medium of claim 1, wherein said probe comprises a fluorescent constituent, the system being such that its fluorescence emission changes as a function of the degree of cure of said curable material.
3. The optical transmission medium of claim 2, wherein the fluorescence emission increases as the degree of cure of the curable material increases.
4. The optical transmission medium of claim 2, wherein the emission decreases as the degree of cure of the curable material increases.
5. The optical transmission medium of claim 1, wherein the fluorescence of said probe is independent of change in the viscosity of said curable material which is a function of the degree of cure of said curable material.
6. The optical transmission medium of claim 1, wherein said probe comprises a phosphorescent material.
7. The optical transmission medium of claim 1, wherein said material system includes a component which functions as a probe.
8. A method of making a coated optical fiber, said method comrpising the steps of:
moving an optical fiber along a path of travel;
applying a material system comprising an ultraviolet light curable coating material having an absorbance which depends on the degree of cure of said curable material and a probe to the optical fiber the probe including a fluorescent constituent which is such that it emits light subsequent to being promoted to an excited electronic state and the system being such that its emission of light changes as a function of cure of the curable coating material, further the degree of overlap of the excitation spectrum of the probe being a function of the behaviour of the absorbance of the curable material as the degree of cure changes;
curing the coating material;
determining the emission of light of the probe constituent to measure the degreeof cure of the curable coating material; and taking up the coated optical fiber.
moving an optical fiber along a path of travel;
applying a material system comprising an ultraviolet light curable coating material having an absorbance which depends on the degree of cure of said curable material and a probe to the optical fiber the probe including a fluorescent constituent which is such that it emits light subsequent to being promoted to an excited electronic state and the system being such that its emission of light changes as a function of cure of the curable coating material, further the degree of overlap of the excitation spectrum of the probe being a function of the behaviour of the absorbance of the curable material as the degree of cure changes;
curing the coating material;
determining the emission of light of the probe constituent to measure the degreeof cure of the curable coating material; and taking up the coated optical fiber.
9. The method of claim 8, wherein said fluorescent probe is such that it is independent of the change in viscosity of said curable material which is a function of the degree of cure of said curable material and the fluorescent emission of said system changes as a function of the degree of cure of the coating material.
10. The method of claim 8, wherein said system comprises at least one coating material and at least one fluorescent probe.
11. The method of claim 8, wherein the said optical fiber comprises an array of optical fibers and said system comprises a matrix material which encloses the array of optical fibers.
12. The method of claim 11, wherein said array is a linear array of optical fibers.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US33065889A | 1989-03-30 | 1989-03-30 | |
| US330,658 | 1989-03-30 |
Publications (2)
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| CA2012263A1 CA2012263A1 (en) | 1990-09-30 |
| CA2012263C true CA2012263C (en) | 1996-07-16 |
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| CA002012263A Expired - Fee Related CA2012263C (en) | 1989-03-30 | 1990-03-15 | Article coated with cured material and methods of making |
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| US (1) | US5037763A (en) |
| EP (1) | EP0390415B1 (en) |
| JP (1) | JP2651036B2 (en) |
| KR (1) | KR0184263B1 (en) |
| CA (1) | CA2012263C (en) |
| DE (1) | DE69033185T2 (en) |
| DK (1) | DK0390415T3 (en) |
| ES (1) | ES2135376T3 (en) |
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| US5182316A (en) * | 1989-05-31 | 1993-01-26 | Minnesota Mining And Manufacturing Company | Fluorescent degree of cure monitors |
| CA2036544A1 (en) * | 1990-02-28 | 1991-08-29 | John Goff | Ultraviolet light curing apparatus and process |
| US5151748A (en) * | 1990-08-07 | 1992-09-29 | The United States Of America As Represented By The Secretary Of Commerce | Optical sensor for the measurement of molecular orientation and viscosity of polymeric materials based on fluorescence radiation |
| DE69131695T2 (en) * | 1990-12-28 | 2001-02-08 | Dow Corning | Process for visualizing the curing of a UV-curable composition by color change |
| US5383776A (en) * | 1992-12-31 | 1995-01-24 | Hoechst Celanese Corporation | Apparatus for analyzing polymer defects |
| US5384079A (en) * | 1993-01-06 | 1995-01-24 | The United States Of America As Represented By The Secretary Of Commerce | Method for detecting thermodynamic phase transitions during polymer injection molding |
| US5418369A (en) * | 1993-03-12 | 1995-05-23 | At&T Corp. | System for continuously monitoring curing energy levels within a curing unit |
| CA2129397C (en) * | 1993-12-21 | 2005-03-22 | Mujibar M. Rahman | Process for manufacturing optical fiber ribbons |
| US5717217A (en) * | 1994-05-05 | 1998-02-10 | Spectra Group Limited, Inc. | Method for determining thickness, degree of cure and other properties of a polymeric coating |
| DE19512483C2 (en) * | 1995-04-04 | 1997-05-15 | Coia Gmbh | Process for the continuous production of a cable element with a circular cross section for the transmission of optical signals |
| DE19512511C2 (en) * | 1995-04-04 | 1997-04-24 | Coia Gmbh | Process for the continuous production of optical waveguide ribbons |
| US5574288A (en) * | 1995-04-17 | 1996-11-12 | Minnesota Mining And Manufacturing Company | Method for measuring residual radiation-curable monomers or oligomers |
| US6052503A (en) * | 1995-09-07 | 2000-04-18 | Dsm N.V. | Optical glass fiber ribbon assembly and radiation curable matrix forming composition |
| US5788374A (en) * | 1996-06-12 | 1998-08-04 | The United States Of America As Represented By The Secretary Of Commerce | Method and apparatus for measuring the temperature of a liquid medium |
| US5958584A (en) * | 1996-07-22 | 1999-09-28 | Dsm Nv | Radiation-curable, optical glass fiber coating composition and optical glass fiber drawing method |
| US5933559A (en) * | 1996-07-22 | 1999-08-03 | Dsm N.V. | Radiation-curable cross-linked ribbon matrix material for bonding an array of coated optical glass fibers |
| JP3955333B2 (en) | 1996-11-08 | 2007-08-08 | デーエスエム アイピー アセッツ ベー．ヴェー． | Radiation-curable optical glass fiber coating composition, coated optical glass fiber, and optical glass fiber assembly |
| FR2766279B1 (en) * | 1997-07-17 | 1999-09-24 | Alsthom Cge Alcatel | PROCESS FOR MANUFACTURING OPTICAL FIBER TAPES |
| USH1843H (en) * | 1997-10-17 | 2000-03-07 | Bur; Anthony J. | Optical sensor for measuring fluorescence anisotropy during polymer processing |
| US5955002A (en) * | 1997-11-12 | 1999-09-21 | Spectra Group Limited, Inc. | Method for determining properties of a polymer coating or film cured by cationic polymerization |
| US6178278B1 (en) | 1997-11-13 | 2001-01-23 | Alcatel | Indoor/outdoor dry optical fiber cable |
| US6110593A (en) | 1998-05-21 | 2000-08-29 | Dsm N.V. | Radiation-curable optical fiber primary coating system |
| US6253012B1 (en) | 1998-11-12 | 2001-06-26 | Alcatel | Cycled fiber lock for cross-functional totally dry optical fiber loose tube cable |
| US6381390B1 (en) | 1999-04-06 | 2002-04-30 | Alcatel | Color-coded optical fiber ribbon and die for making the same |
| US6456895B1 (en) * | 1999-09-13 | 2002-09-24 | Fitel Usa Corp. | Method and apparatus for detecting conditions in a UV curing lamp system |
| US6836362B2 (en) | 2001-05-14 | 2004-12-28 | General Electric Company | Method for the rapid determination of the optical quality of combinatorial libraries |
| KR20020096449A (en) * | 2001-06-20 | 2002-12-31 | 삼성전자 주식회사 | Apparatus for drawing optical fiber with coating hardness measuring device |
| EP1438568A2 (en) | 2001-10-16 | 2004-07-21 | Valspar Sourcing, Inc. | Method of monitoring extent of cure of a coating |
| US6702453B2 (en) | 2001-10-26 | 2004-03-09 | Birchwood Lighting, Inc. | Flexible light fixture |
| CN1636041A (en) * | 2001-10-31 | 2005-07-06 | Dsmip财产有限公司 | Radiation-curable compositions and related methods for the assembly and repair of optical components and products prepared thereby |
| US6932869B2 (en) * | 2001-11-15 | 2005-08-23 | Alcatel | UV-cure of coating for optical fiber assisted by ultrasound |
| JP4185939B2 (en) | 2006-03-15 | 2008-11-26 | オムロン株式会社 | UV curable resin state estimation method |
| JP5040380B2 (en) * | 2007-03-13 | 2012-10-03 | オムロン株式会社 | Ultraviolet irradiation system, curing reaction detection device used therefor, and method for curing ultraviolet curable resin using the same |
| US20110108411A1 (en) * | 2009-11-11 | 2011-05-12 | Popik Vladimir V | Methods for labeling a substrate using a hetero-diels-alder reaction |
| EP3568689A1 (en) | 2017-01-10 | 2019-11-20 | Sun Chemical Corporation | In-line coating weight and radiant energy exposure measurement |
| US10385144B2 (en) | 2017-07-28 | 2019-08-20 | Xerox Corporation | In-situ evaluation of curing of ink compositions via absorbance spectroscopy |
| CA3087475A1 (en) * | 2018-01-15 | 2019-07-18 | Prysmian S.P.A. | An optical fiber ribbon and a method and system of producing the same |
| AT525543B1 (en) * | 2022-05-16 | 2023-05-15 | Medek & Schoerner Gmbh | Fiber optic ribbon and method of making same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6049146B2 (en) * | 1981-07-04 | 1985-10-31 | 日本電信電話株式会社 | Coating materials for optical glass fibers |
| US4444701A (en) * | 1982-07-21 | 1984-04-24 | Meguiar Floyd L | Mold release agent composition and improved molding method |
| US4474830A (en) * | 1982-12-29 | 1984-10-02 | At&T Bell Laboratories | Multiple coating of fibers |
| US4547040A (en) * | 1983-06-21 | 1985-10-15 | Mitsubishi Rayon Co., Ltd. | Optical fiber assembly and process for preparing same |
| US4548771A (en) * | 1984-01-30 | 1985-10-22 | Battelle Memorial Institute | Ultrasonic vulcanization |
| JPS61158302A (en) * | 1984-12-28 | 1986-07-18 | Dainichi Nippon Cables Ltd | Optical fiber |
| JPS61215236A (en) * | 1985-03-15 | 1986-09-25 | Nippon Paint Co Ltd | Composition for coating optical fiber |
| US4651011A (en) * | 1985-06-03 | 1987-03-17 | At&T Technologies, Inc. | Non-destructive method for determining the extent of cure of a polymer |
| JPH064252B2 (en) * | 1985-06-17 | 1994-01-19 | 株式会社明治ゴム化成 | Hose continuous vulcanization method |
| US4798346A (en) * | 1986-12-05 | 1989-01-17 | American Telephone And Telegraph Company - At&T Technologies, Inc. | Method of and apparatus for taking up lightguide fiber |
-
1990
- 1990-03-15 CA CA002012263A patent/CA2012263C/en not_active Expired - Fee Related
- 1990-03-21 ES ES90303050T patent/ES2135376T3/en not_active Expired - Lifetime
- 1990-03-21 EP EP90303050A patent/EP0390415B1/en not_active Expired - Lifetime
- 1990-03-21 DK DK90303050T patent/DK0390415T3/en active
- 1990-03-21 DE DE69033185T patent/DE69033185T2/en not_active Expired - Fee Related
- 1990-03-28 JP JP2077171A patent/JP2651036B2/en not_active Expired - Fee Related
- 1990-03-29 KR KR1019900004216A patent/KR0184263B1/en not_active IP Right Cessation
- 1990-09-05 US US07/579,220 patent/US5037763A/en not_active Expired - Fee Related
Also Published As
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| JPH0323240A (en) | 1991-01-31 |
| JP2651036B2 (en) | 1997-09-10 |
| EP0390415B1 (en) | 1999-06-30 |
| ES2135376T3 (en) | 1999-11-01 |
| DK0390415T3 (en) | 1999-11-22 |
| DE69033185T2 (en) | 1999-12-16 |
| US5037763A (en) | 1991-08-06 |
| EP0390415A1 (en) | 1990-10-03 |
| DE69033185D1 (en) | 1999-08-05 |
| KR0184263B1 (en) | 1999-04-15 |
| KR900014908A (en) | 1990-10-25 |
| CA2012263A1 (en) | 1990-09-30 |
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