CA1221795A - Optical fiber cladding - Google Patents

Optical fiber cladding

Info

Publication number
CA1221795A
CA1221795A CA000422209A CA422209A CA1221795A CA 1221795 A CA1221795 A CA 1221795A CA 000422209 A CA000422209 A CA 000422209A CA 422209 A CA422209 A CA 422209A CA 1221795 A CA1221795 A CA 1221795A
Authority
CA
Canada
Prior art keywords
weight
acrylate
highly fluorinated
fluorinated monofunctional
synergist
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
Application number
CA000422209A
Other languages
French (fr)
Inventor
Bolesh J. Skutnik
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ensign Bickford Optics Co
Original Assignee
Ensign Bickford Optics Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ensign Bickford Optics Co filed Critical Ensign Bickford Optics Co
Application granted granted Critical
Publication of CA1221795A publication Critical patent/CA1221795A/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C25/00Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10Coating
    • C03C25/104Coating to obtain optical fibres
    • C03C25/105Organic claddings
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/045Light guides
    • G02B1/048Light guides characterised by the cladding material

Abstract

ABSTRACT OF THE DISCLOSURE
Optical fiber cladding compositions, based on highly fluorinated monofunctional acrylates, yield hard clad fibers that have attenuations often below 10 dB/km and whose temperature behavior is superior to silicone plastic clad silica (PCS). The numerical aperture (NA) of the fiber can be varied by selecting a particular composition. The main components of the composition are (1) a highly fluorinated monofunctional acrylate with a refractive index below 1.38; (2) a trifunctional or higher acrylate that serves as a cross-linking agent; (3) a mono or polyfunctional thiol that functions as a synergist;
and (4) a photoinitiator such as an ultraviolet (UV) initiator. These com-ponents can be varied relative to one another over a wide range, but the fluoroacrylate must always be the major component. Where the fluoroacrylate is a solid at room temperature, a small amount of solvent like di-isobutyl ketone or methylene chloride can be added.

Description

~2~L79~;

The present invention relates to cladding compositions for apical fibers, and more particularly to ultraviolet (W) curable compositions con-twining a highly fluorinated monofunctional acrylate as the major component and which are useful to produce superior hard clad optical fibers whose attenuation is comparable with a silicone cladding and whose low temperature attenuation increase is significantly less than with a silicone cladding.
Currently, plastic clad silica (PUS) optical fibers mean a silicone cladding over a fused quartz core. The viscosity and curing requirements of the silicones restrict the production rate to about 0.5 meter/second. The silicone cladding does not adhere well to the quartz, and since it is also soft, the clad fiber is hard to connect. Thermal changes in the fiber's environment can cause a pumping action at the connection, where the quartz core is forced in and out of the clamped cladding. Furthermore, exposing these PUS fibers to low temperatures in the -40 to -50C range often yields an attenuation increase of 10-20 dB/km. In many cases, an increase in room temperature attenuation also occurs after thermal cycling. Typical results are given below:
A 200 em Suprasil* fiber with General Electric 670 silicone resin and a soft urethane jacket (Goodrich* 58880) -Attenuation ~dB/km) Room Temp. Start 10.5 after 3 cycles 10.9 -46 C sty cycle 18.6 3rd cycle 20.2 ~75 C sty cycle 9.6 3rd cycle 10.0 Example 2: Same as above except Dow Corning's Sylgard* 184 silicone resin is used instead of the General Electrical resin -*Trade mark .

Sue Attenuation (dB/km) Room Temp. Start 10.6 after 2 cycles 12.2 -46 C sty cycle 24.5 end cycle 26.6 +75 C sty cycle 9.0 end cycle 10.3 Optical fibers have been made with various W curable resins as protective coatings. See, for example United States Patent IT 4,125,644 to Arthur D, Kettle et at and United States Patent No. 4,099,837 to Vazirani.
See also Shelf et at, "US Cured Resin Coating for Optical Fiber/Cable", Pro.
Thea International Wire and Cable Swamp., pp. 327-332 ~1979), and Vazirani et at, US Cured Epoxy-Acrylate Coatings on Optical Fibers I. Chemistry and Application", paper Tub at the Topical Meeting on Optical Fiber Transmission II, February 22-24, 1977, Williamsburg, Virginia.
W curable compositions can be cured quickly into hard, flexible coatings. However, these compositions are normally made up of multi functional acrylates and other chemicals whose refractive indices range from 1.46 to 1.55, which is above the refractive index for fused quartz, 1.458~ at room tempera-lure. To function as an optical fiber cladding, the refractive index of the cladding must be lower than that of the quartz core at all operating temperatures. The refractive index increases as the temperature decreases roughly in proportion to the densification of the material. Quartz has a very low thermal contraction coefficient and thus its refractive index increases much slower than plastics, especially above the plastics' glass transition temperature.
While other fluorinated polymers have been tried as cladding for optical fibers see Buyer et at, SUE ANTIC Pro. 23, 383 ~1977)), it has not heretofore been known to use a fluoroacrylate polymer as a cladding material.
Moreover, it has not hereto before been known to use highly fluorinated monomers ~L~2~3S

as precursors of any type of optical coating. Lyle fluorinated monofunctional acrylates have been recommended for textile treatments to increase their resistance to water, oil and grease. The acrylate monomers are usually polyp merited in the treated fabric to yield medium molecular weight polymers grafted to the fabric.
The present invention seeks to provide a hard clad optical fiber which exhibits low loss and is temperature stable.
This invention also seeks to provide a cladding composition for optical fibers which is both optically and mechanically superior to silicone cladding.
The invention further seeks to provide an W curable optical fiber coating having a refractive index lower than that of the quartz core which, being hard, facilitates connections.
According to one aspect of the present invention there is provided a cladding composition for plastic clad silica optical fibers comprising a highly fluorinated monofunctional acrylate with a refractive index below 1.38 and constituting more than 50% by weight of the composition a polyfunctional acrylate being trifunctional or higher serving as a cross linking agent, a moo or polyfunctional they'll that functions as a synergism, and a photo initiator.
According to another aspect of the present invention there is pro-voided a plastic clad silica optical fiber comprising a fused silica core, and an ultraviolet cured cladding composition which includes a mixture of a highly fluorinated monofunctional acrylate with a refractive index below 1.38 and constituting more than 50% by weight of the composition, a trifunctional or higher acrylate serving as a cross linking agent, a moo or polyfunctional they'll that functions as a synergism, and an ultraviolet initiator.
The invention provides a series of compositions, based on highly ,., 1 Jo fluorinated monofunctional acrylates, which yield hard clad fibers that 'Noel attenuations often below 10 dB/km and whose temperature behavior is thus superior to silicone PUS fibers. The numerical aperture (via) of the fiber, i.e. the measure of the acceptance angle, can be varied by selecting a part-cuter composition. Depending on the quality of the glass core, attenuations in the ~-10 dB/km range are possible. This is in contrast to the lowest attenuation of commercially available hard clad PUS fibers of 25 to 40 dB/km in the same wavelength region, i.e. 800 em.
The main components of the composition are (1) a highly fluorinated monofunctional acrylate with a refractive index below 1.38; (2) a trifunctional or higher acrylate that serves as a cross linking agent; (3) a moo or polyp functional, they'll that functions as a synergism; and (4) a photo initiator such as an W initiator. These components can be varied relative to one another over a wide range, but the fluoroacrylate must always be the major component, i.e. greater than 50% by weight. Where the fluoroacrylate is a solid at room temperature, it is sometimes useful to add a small amount, say 5 to 15%
by weight, of a solvent like di-isobutyl Cowan or ethylene chloride.
The compositions according to the invention, when applied to quality fused silica core, yield a low loss, temperature stable PUS optical fiber.
Since it is possible to tailor the refractive index, the NO of the clad fiber can be adjusted in a wide range, from about 0.1 to 0.4. The compositions of the invention adhere to glass better than silicone and cure faster than silicone.
As a result, clad PUS fibers can be produced with faster line speeds, and because the cladding is hard, reliable connections are facilitated. In con-tryst to thermoplastic cladding which must be extruded or solvent-coated onto the fiber core, the compositions of this invention, being fluids, permit dip coating thereby reducing dangers of stress or contamination from extrude ~Z~7~3~

equipment or high solvent levels.
The hard clad optical fibers produced using the compositions of the invention have better radiation resistance than glass clad fibers because the fused silica core, which can be used with the compositions of tune invent lion, is the least sensitive type of glass. Compared to glass clad fibers, it is easier to fabricate large core fibers, i.e. greater than 400 em diameter, with good bending strength. Moreover, it is possible to apply continuous, concentric, thin cladding to even larger diameter fiber cores.
As compared to the prior art especially the Kettle et at and Vazirani patents swooper, the major component of the optical fiber cladding come positions according to the invention is a monofunctional monomer. In the preferred form, a monthly based on a Solon is used. Besides the lowered functionality, it represents another class of low odor thiols. Further, the compositions of the invention can be applied at room temperature, even with solid components by the addition of small amounts of solvents without any dotter-mental effects on the optical properties. The change in refractive index upon curing is small, 0.02 to 0.03 units, compared to acrylate manufacturers' reported gains of 0.05 to 0.08 units. The use of small amounts of a polyphonic-tonal additive in conjunction with primarily monofunctional monomers and the they'll synergism yields a thermoses with much better thermal stability than a thermoplastic fluoroacrylate.
Combinations of the four components of the compositions of the invention are chosen in general so as to achieve a refractive index of the mix-lure that is lower than 1.42. In practice) the combination is chosen so as to yield a NO for the clad fiber in the range desired for the particular apply-cation. General guidelines for each component are set forth below.
The highly fluorinated monofunctional acrylate with a refractive , ~2~7~.~
index below 1.38 is one in which more than 50% of the compounds molecular weight comes from the fluorine atoms. Typical compounds have the general formula:
RF(cH2)no2cc2ll3 where RF = X~(CF2)m' m = 3-12 X = H or F and n = l or 2 The polyfunctional acrylate should be trifunctional or higher and for the lowest loss clad fibers should be selected from among the smallest such compounds as for example trimethylol propane triacrylate.
The they'll synergism can be any of a large number of compounds as long as its refractive index is below about 1.55. The preferred compounds are the esters of Marquette containing acids such as thio-glycolic acid and 2- or Marquette prop ionic acid esters. The most preferred they'll compounds are they'll containing sullenness such as ~-mercaptopropyl trimethoxy Solon.
Various photosensitizes and photo initiators are well-known to those skilled in the art, but as with the other components, those operable in this invention would have a refractive index below about 1.55. Of particular interest are the highly reactive compounds such as 2 hydroxy, 3 methyl, l-phenylpropanone; methyl, ethyl, propel or isobutyl ethers of Bunsen and other anal logs, and 2,2-dimethoxy, 2-phenylacetophenone.
In general, the weight % ranges of the four components that satisfy this invention and the preferred ranges may be tabulated as follows:
Preferred Particularly Range Preferred Range Fluoroacrylate50-90% 60-90% 60-80%
Polyacrylate2-35% 5-25% 5-25%
They'll synergism 0.5-20% 3-10% 3-10%
Photoinitiator0.5-20% 0.9-10% 1-10%

I

Table I lists a number of possible compositions and the most sign-ficant properties. It is possible to obtain a range of numerical apertures by varying the components, while all silicone clad fibers have a numerical aperture of 0.32-0.33.

.

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ED I ox o I
n l on It .

try n I
--n x o -h Z V in to I o a>
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I, h h O En E-- so D h h a) o O g Jo I 0 C O
I O O Pi h Jo h a o :~: o o P, I, a> o cC ' O h So O O I Pi MY Z
I h o S or ho ho CUD h I_. v a a in Z'. o ado ted h O h h I, in to G to Hi t to rl us:: rl US h rl h rl to rl to rl i-l I' I in US: pi I tlH I) I
O h h , , Al lo 9~5 Table II represents representative data of thornily cycling tests and room temperature attenuations for some compositions. For comparison sample results are also given for a few silicone clad fibers. In all these examples the clad fiber is jacketed with a soft urethane, Goodrich* 58880, and the optical measurements are made at 820 em with a launch I for the light source of 0.25. State of the art techniques well-known in the optical fiber field were used to coat the fiber cores and standard W lamps at 80 watts/cm were used to cure the fluoroacrylate coatings at speeds between 25 to 80 m/min.
Use of more powerful lamps would allow even faster speeds, while the use of less powerful lamps would require slower speeds.

TABLE II
A. Thermal Cycling CompositionTemperatureAttenuation (dB/km) 3 Room Temp.Start 9.9 After cycles 9.4 -46~C 12.9 ~75C 8.6 12 Room Temp.Start 16.6 After cycles 14.3 -46C 14.5 ~75C 11.7 General Electric Room Temp.Start 10.5 After cycles 10.9 RTV*-670 -46C 18.6 *75C 9.6 Dow Corning - Room Temp.Start 10.6 After cycles 12.2 Sylgard* 184 -46C 24.5 ~75C 9.0 B. Representative Room Temperature Results Com~osition~easured NAAttenuation (dB/km) 1 .37 10.7
2 .38 8.4
3 .33 9.1 11 .37 8.0 12 .36 8.5 13 .33 8.2 Sylgard* 184 .33 8.2 Sylgard* 182 .33 go RTV*-670 .33 8.1 *Trade mark go I

The room temperature data show that the 'nerd clad gibers made loath compositions of this invention have comparable attenuation to that achieved with silicone clad fibers. The thermal cycling data clearly demonstrate that the hard clad fibers are much less affected by temperature changes then. tune silicone clad fibers. This is a great technical advantage of the invention.
A most important advantage of the invention is the enhanced ability to collect the hard clad fibers as compared to silicone clad ones. The hard clad fiber is superior in making terminations and connections. This is attributed to the superior adhesion of the fluoroacrylate cladding to the fused silica core.
The other advantages over silicone PUS fibers include the increases possible in processing over a silicone cladding. Here the fluoroacrylate cladding composition can be applied and cured at 40-80 meters/min with 80 watts/
cm US lamps, whereas the silicone cladding rarely can be applied and cured above 25 meters/min.

. .

Claims (8)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A cladding composition for plastic clad silica optical fibers com-prising a highly fluorinated monofunctional acrylate with a refractive index below 1.38 and constituting more than 50% by weight of the composition, a polyfunctional acrylate being trifunctional or higher serving as a crosslinking agent, a mono or polyfunctional thiol that functions as a synergist, and a photoinitiator.
2. The composition according to Claim 1 wherein said highly fluorinated monofunctional acrylate comprises 50 to 90% by weight, said polyfunctional acrylate comprises 2 to 35% by weight, said thiol synergist comprises 0.5 to 20% by weight, and said photoinitiator comprises 0.5 to 20% by weight.
3. The composition according to Claim 1 wherein said highly fluorinated monofunctional acrylate comprises 60 to 90% by weight, said polyfunctional acrylate comprises 5 to 25% by weight, said thiol synergist comprises 3 to 10%
by weight, and said photoinitiator comprises 0.9 to 10% by weight.
4. The composition according to claim 1 wherein said highly fluorinated monofunctional acrylate comprises 60 to 80% by weight, said polyfunctional acrylate comprises 5 to 25% by weight, said thiol synergist comprises 3 to 10%
by weight, and said photoinitiator comprises 1 to 10% by weight.
5. The composition according to Claim 1, 2 or 3 wherein said highly fluorinated monofunctional acrylate has the general formula:
RF(CH2)nO2CC2H3 where RF is X-(CF2)m, m is an integer from 3 to 12, X is H or F, and n is 1 or 2.
6. The composition according to Claim 1, 2 or 3 wherein said highly fluorinated monofunctional acrylate is trihydroperfluoroundecylacrylate, said polyfunctional acrylate is trimethylolpropanetriacrylate, and said thiol synergist is ?-mercaptopropyltrimethoxysilane.
7. The composition according to Claim 1, 2 or 3 wherein said highly fluorinated monofunctional acrylate is trihydroperfluoroheptylacrylate, said polyfunctional acrylate is trimethylolpropanetriacrylate, and said thiol synergist is 3-mercaptoproprionate.
8. A plastic clad silica optical fiber comprising a fused silica core, and an ultraviolet cured cladding composition which includes a mixture of a highly fluorinated monofunctional acrylate with a refractive index below 1.38 and constituting more than 50% by weight of the composition, a trifunc-tional or higher acrylate serving as a crosslinking agent, a mono or poly-functional thiol that functions as a synergist, and an ultraviolet initiator.
CA000422209A 1982-02-24 1983-02-23 Optical fiber cladding Expired CA1221795A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US35205082A 1982-02-24 1982-02-24
US352,050 1982-02-24

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AU (1) AU569145B2 (en)
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