CN86100210A - The treatment process of preform for optical fiber - Google Patents

The treatment process of preform for optical fiber Download PDF

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Publication number
CN86100210A
CN86100210A CN198686100210A CN86100210A CN86100210A CN 86100210 A CN86100210 A CN 86100210A CN 198686100210 A CN198686100210 A CN 198686100210A CN 86100210 A CN86100210 A CN 86100210A CN 86100210 A CN86100210 A CN 86100210A
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preform
transparent glass
optical fiber
dehydration
treatment process
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古井泰郎
松原邦弘
饭野星
小粥干夫
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Furukawa Electric Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/01Manufacture of glass fibres or filaments
    • C03B37/012Manufacture of preforms for drawing fibres or filaments
    • C03B37/014Manufacture of preforms for drawing fibres or filaments made entirely or partially by chemical means, e.g. vapour phase deposition of bulk porous glass either by outside vapour deposition [OVD], or by outside vapour phase oxidation [OVPO] or by vapour axial deposition [VAD]
    • C03B37/01446Thermal after-treatment of preforms, e.g. dehydrating, consolidating, sintering

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  • Geochemistry & Mineralogy (AREA)
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  • Organic Chemistry (AREA)
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Abstract

A kind of method that preform for optical fiber is handled, so that the transmission characteristics that the photoconductive fiber that makes has in 1.2 to 1.6 micron wave lengths is equal to or less than 5 decibels/km, comprise: in advance the porous silica preform is carried out processed, the material that such processed is crossed carries out the transparent glass processing then, thereby avoids increasing the peak in the loss of 1.52 micron wave strong points.

Description

The treatment process of preform for optical fiber
The present invention relates to the porous soot matter preform dehydration that photoconductive fiber uses and the treatment process of transparent glassization, more particularly, is a kind of relating to handle this preform, so that obtain not exist the fibre-optic method of the loss increase that hydrogen causes.
General fork-like farm tool used in ancient China is said, makes photoconductive fiber porous soot matter preform by quartz and forms with VAD method (vapour phase axial deposition technique) and OVPO method (outer vapour phase oxidation process).Then, this porous soot matter preform is through dehydration and transparent glass processing and become fibre-optic transparent preform.
The means of dehydration of porous soot matter preform and transparent glass processing are at United States Patent (USP) the 3rd, 933, No. 454 invention (hereinafter referred to as prior art 2) is open, the means of inventing before above-mentioned patent are then at United States Patent (USP) the 3rd, 459, No. 522 invention (hereinafter referred to as prior art 1) is open.
In prior art 2, be to add glass soot that the water decomposition reaction produces by flame to assemble and form as hole soot matter preform more than the process object.And such porous soot matter preform dewatered in containing the atmosphere of chlorine and the transparent glass processing simultaneously.
Handling preform and obtaining fibre-optic occasion with prior art 2, its transmission characteristics is about 10 decibels/km (dB/km) in 650 to 1100 millimicrons of (nm) wave bands, but presents an absorption peak at 950 millimicrons of wavelength.
On the other hand, be to add water decomposition reaction means production porous soot matter preform in addition in the prior art 1 with flame, the dehydration of this porous soot matter preform is to carry out in atmosphere containing chlorine, and the preform after the dehydration then carries out the transparent glass processing in non-atmosphere containing chlorine.So its feature is exactly so-called " processing of two operations " method.
In prior art 1, preform dewaters and the transparent glass processing divides one of reason that two operations carry out to be based on economically consideration.Other reasons then are based on, and the preform long period is exposed to and has a large amount of chlorine in the atmosphere containing chlorine and stagnate among preform, and this just might cause in this glass and crack.
Yet the fork-like farm tool used in ancient China that its transmission characteristics of glass that prior art 1 is handled is handled than prior art 2 must be poor.
And, prior art 2 once was described because following reason in relevant prior art 1, be not suitable for the dehydration that adds the porous soot matter preform that the water decomposition reaction obtains by flame.
Promptly a large amount of chlorine in the atmosphere containing chlorine that is adopted in prior art 1 can make porous soot matter preform produce pore in next step is handled, and the pollutent that contains in the chlorine of commercially available purity can be exceeded tolerance range and imports among this glass.
In addition, in prior art 1, porous soot matter preform after the indoor dehydration of chlorine treatment, when the preform that has dewatered from chlorine gas chamber move into that transparent glassization uses solidify the chamber time, moisture may invade among the preform once more.
In addition, if preform can dewater and the transparent glass processing simultaneously, then with prior art 1 in two operation method comparisons can improve economical effectiveness.
These backgrounds are exactly 2 pairs of dehydrations of prior art and these two motivations that operation is carried out simultaneously of transparent glass processing.
As everyone knows, if hydrogen (H 2) spread and be absorbed among the photoconductive fiber, its transmission characteristics can degenerate in the aged mode, but the technical process relevant with correcting countermeasure in " Nikkei electron " (on December 3rd, 1984 is at Japanese publication) be entitled as " loss that hydrogen causes in the settled photoconductive fiber increases problem 1; 2; fibre-optic loss increases problem " and disclose in detail, and the loss that causes as hydrogen so far increases the peak and what noticed is 1.39 microns and the absorption peak of 1.41 micron wave lengths that Si OH and Ge OH are arranged, hydrogen molecule is at the absorption peak of 1.24 micron wave lengths, and the loss of fitting about hydrogen in addition increases the important research report at peak and do not see as yet.
But, had been found that in the research of the present inventor about the photoconductive fiber transmission characteristics that an important loss that did not disclose as yet increases the peak, promptly except above-mentioned is at the absorption peak of 1.52 microns of wavelength.
This absorption peak of 1.52 microns is considered to be caused by the Si-H absorption of vibrations.
Experience according to people of the present invention, the behavioural characteristic of finding above-mentioned absorption peak is when this photoconductive fiber has stood 80 ° to 100 ℃ temperature in the operation of making optical fiber cable, this peak just easily takes place, and this peak just has the trend that slowly reduces after in a single day presenting.
Fig. 3 has shown 1.52 microns of wavelength and has located the actual fibre-optic loss spectra that absorption loss increases that produced.
From Fig. 3 as seen, the feature that this absorption peak presents is that this absorption peak occurs at 1.55 micron wavebands, and the loss at 1.39 and 1.24 micron waveband places also increases simultaneously, thereby is understandable that transmission characteristics will worsen at 1.2 and 1.6 microns places.
This absorption peak can become in 5 decibels/the photoconductive fiber below the km at 1.2 to 1.6 microns places of wavelength at transmission characteristics, it is the problem that to discern, in transmission characteristics and wavelength region, find the prior art 2 so can not resemble, and its transmission characteristics is also than in the also poor prior art 1 of prior art 2 being unpredictable item fully.
Therefore, one object of the present invention is exactly to have considered above-mentioned shortcoming and problem, a kind of method of handling preform for optical fiber is provided, thereby can obtains a kind of photoconductive fiber, and it can not be created in the hydrogen loss increase peak that 1.52 microns of wavelength are located to occur.
The invention provides a kind of method that preform for optical fiber is handled, make rich silicon-dioxide soot matter porous preform dehydration and transparent glassization, and obtain having the preform for optical fiber that 5 decibels/km or littler transmission characteristics are arranged in 1.2 to 1.6 micron wave strong points, in this treatment process, earlier preform is dewatered, and then carry out transparent glassization to this preform, so that these two operations are separately carried out.Said dehydration procedure comprises: by helium He, oxygen O 2And dehydrated air and the dehydration atmosphere that forms; The dehydration reaction in fact that treatment temp is set in porous soot matter preform begins more than the temperature, but is lower than independent closed pore formation temperature; Make the treatment temp zone of this porous soot matter preform by above-mentioned dehydration atmosphere.Said transparent glass chemical industry preface comprises: form helium He, oxygen O 2It perhaps only is the transparent glass gasification atmosphere of helium He; Set treatment temp to more than the minimum transparent glass temperature, make dehydration procedure preform afterwards by the treatment temp zone in the above-mentioned vitrifying atmosphere.
In the method for the invention, owing to separately dewater and transparent glass chemical industry preface, when the porous soot matter preform of being produced by VAD method or OVPO method dewaters with the transparent glass processing in predetermined atmosphere respectively, preform residual amount of chlorine after transparent glassization becomes very small, just can make the photoconductive fiber with good transmission characteristics from such preform.
In more detail, porous soot matter preform is dewatered in same operation simultaneously and the method for transparent glass processing in, the transparent glassization of preform is carried out in atmosphere containing chlorine.Therefore, the residual chlorine increase causes the defective in the glass structure in the preform of transparent glassization, and the mechanism owing to set hydrogen causes that the loss that is caused by hydrogen increases again.But the present invention separately carries out this two operation, so there is not this problem.
In dehydration procedure of the present invention, atmosphere is by helium He and oxygen O 2And dehydrated air (chlorine, thionyl chloride, silicon fluoride, etc.) form, treatment temp then is set in fact dehydration reaction, and to begin temperature above and be lower than independent closed pore formation temperature.
The processed temperature is set in fact, and dehydration reaction begins more than the temperature and is lower than the reasons are as follows of independent closed pore formation temperature:
Be that the lower limit of processed temperature is located in fact dehydration reaction to begin the above reason of temperature be that when this treatment temp was lower than the processed lowest temperature, effectively dehydration obviously can not be carried out.And the processed upper temperature limit is set in the reason that is lower than independent closed pore formation temperature be, when this treatment temp is higher than this temperature, the sintering of porous soot matter preform can be excessive, thereby produce the independent closed pore of this preform, make chlorine enclose pore and cause the problem that the loss that caused by hydrogen increases.
The present invention is with helium He, oxygen O to the operation that preform carries out transparent glassization 2Or singly be that helium He forms atmosphere and treatment temp is set in more than the minimum transparent glass temperature.
Because this atmosphere do not contain chlorine, so in the occasion of preform transparent glassization, glass can not generate defective.Because treatment temp is more than the transparent glass temperature, the homogeneity of glass ingredient is improved, thereby fibre-optic transmission characteristics is improved again.
Like this, can obtain having the photoconductive fiber of good transmission characteristics from the preform of handling according to method of the present invention, and because the preform treatment condition are very suitable, the photoconductive fiber that is obtained can not produce 1.52 micron wave strong points and the loss increase peak that hydrogen causes occur.This point just can be seen from the detailed description of the following example.
From the following open explanation of carrying out with reference to accompanying drawing, and by the pointed novelty of the present invention of claims, with above-mentioned and other is about purpose of the present invention and characteristics as can be seen.
Fig. 1 is an expression preform for optical fiber treatment process and according to the synoptic diagram of the inventive method institute using appts;
Fig. 2 uses the suitable temperature ranges synoptic diagram of chlorine as dehydrated air in expression the inventive method;
Fig. 3 is expression 1.55 micron waveband loss spectra synoptic diagram; And
Fig. 4 uses SiF in expression the inventive method 4Suitable temperature ranges synoptic diagram as dehydrated air.
Followingly the embodiment that the present invention handles the preform for optical fiber method is described in detail with reference to the accompanying drawing fork-like farm tool used in ancient China.
Fig. 1 has represented to be used in the device of the inventive method.Reference number among Fig. 1 [1] has been pointed out an electric furnace, and numeral [2] has been pointed out the muffle tube of electric furnace [1], and numeral [3] has been pointed out the carbon heater of stove [1].
Muffle tube [2] has the gas feed [4] in position, its underpart, and has the pneumatic outlet of position [5] at an upper portion thereof.
Reference number [6] has been pointed out the porous silica soot matter preform made by VAD method or OVPO method, and this preform is then supported by silicon-dioxide support rod [7].
In Fig. 1, when preform [6] is dehydrated, helium He, oxygen O 2And/or dehydration gas (for example, chlorine Cl 2) enter into muffle tube [2] by import [4] and make muffle tube [2] be in the atmosphere of regulation.Treatment temp (actual temperature) is set to about 900 ° to 1300 ℃ by well heater [3], make treatment temp in the muffle tube [2] be set in fact dehydration reaction begin temperature above, below the independent closed pore formation temperature.
Preform [6] inserts from muffle tube [2] upper end, is moved down into the processed humidity province with suitable speed then, thereby makes this preform begin to carry out successively processed from its lower end.
Preform [6] has just become sintering state by this processed.Because treatment temp at this moment is lower than independent closed pore formation temperature as mentioned above, so the not sealing of the hole of preform [6], so preform [6] is not the dehydrated air (Cl that enters in the hole 2) directly enclose wherein.
Preform after the processed [6] carries out the transparent glass processing with electric furnace shown in Figure 1 [1] or other preparation with the similar electric furnace of Fig. 1.
When then preform being carried out the transparent glass processing after the processed with this electric furnace [1], feed muffle tube [2] so that fully exclude dehydrated air with removing gas in advance, and upwards promote the preform that has dewatered from muffle tube [2] from its inside.
When using other electric furnace to carry out to the processing of preform transparent glass, be used for the electric furnace that preform carries out processed and transparent glass processing is arranged in the casing that degree of purification is higher than preset value, the preform that has dewatered in dehydration furnace moves on in the stove of transparent glass processing, and this preform that dewatered is placed on the top of preform transparent glass stove muffle tube.
Then, feed helium He and oxygen O from import [4] to muffle tube [2] 2Perhaps only be helium He, so that keep predetermined atmosphere in the muffle tube [2]; To manage [2] middle treatment temp (actual temperature) simultaneously and be set to about 1350 ° to 1650 ℃, so that the treatment temp in the pipe [2] reaches more than the minimum transparent glass temperature by well heater [3]; The muffle tube [2] that the preform [6] that will dewater then feeding is such makes it move down (falling) to the transparent glass humidity province with suitable speed, thereby makes the preform that dewaters [6] begin to carry out successively the transparent glass processing from its lower end.
Like this, preform [6] has just been finished processed and transparent glassization.
When preform [6] carried out the transparent glass processing, the processing speed (translational speed) of preform in muffle tube [2] be lower velocity preferably, so that obtain good transmission characteristics.For example, speed is 100 millimeters/hour.
In the transparent glass processing, treatment temp is had no particular limits, but because muffle tube [2] will be by melting in about 1700 ℃ of temperature, so preferably 1650 ℃ of the treatment temp upper limits in fact.
Then, the experimental example of the inventive method will be narrated below.
Below among Xu Shu the embodiment, the preform of producing by the VAD method and single mode (single) the mode transmission photoconductive fiber made has the core of 9 micron diameters, the pure silicon dioxide coating layer and △=0.3% of 125 micron diameters.One of testing method example is, photoconductive fiber put in the hydrogen of 100 ℃ of temperature to keep 15 minutes, takes out this photoconductive fiber then and measures its loss spectra respectively.The loss that is caused by hydrogen of these fibers is increased characteristic to be compared with original loss characteristic and judges.
Used wavelength is 1.52 microns during evaluation.
Table 1 and table 2 have been listed the experimental data of porous soot matter preform being carried out the dehydration and the transparent glass processing of various different conditions, single mode (single) photoconductive fiber that obtains from this preform is estimated, the optimum condition of each processing is also discussed.
Figure 86100210_IMG1
Figure 86100210_IMG2
Treatment process I in the table 1 is to dewater simultaneously and transparent glass chemical industry preface, and the treatment II in the table 2 then is separately to dewater and transparent glass chemical industry preface.
More than each treatment process all be to implement with electric furnace shown in Figure 1.
In the table 2, the treatment temp when T1 represents to dewater, the treatment temp when T2 represents transparent glass.
The result that table 1 and table 2 are enumerated shows that the hydrogen that the treatment process I is caused causes the loss increase to get greatly than treatment II fork-like farm tool used in ancient China.
The reason that the treatment process I causes loss that hydrogen causes to increase is to carry out the transparent glass processing in chlorine-containing gas because of porous soot matter preform, and in the defective of defective that forms owing to residual chlorine in the residual chlorine in the glass, glass structure and glass structure set hydrogen etc. all should consider.And why treatment II does not increase that the reason of loss can be thought because processed and transparent glass chemical industry preface are separately carried out, so not generation of the problem that occurs in the treatment process I.
On the other hand, even in the method II, the photoconductive fiber of sample a and b is also observed the difference on the characteristic.
This has just pointed out, if the treatment temp (relation also being arranged with the treatment time) of treatment II is further studied, more suitably treatment condition still exist.
From this viewpoint, following experiment is carried out in order to try to achieve optimal treatment condition in the treatment II.
Parameter in the experiment is listed in table 3.In these experiments, each parameter is numerically carried out various combination, porous soot matter preform is dewatered and the transparent glass processing, and the preform of handling is made photoconductive fiber through wire drawing, then it has been carried out owing to adding the test that hydrogen causes loss to increase.
Figure 86100210_IMG3
Figure 86100210_IMG4
Temperature in the table 3 is an actual value, and the supply of protection gas is: the He=65 liter/minute, O 2=6.5 liters/minute, and Cl 2=0.65 liter/minute.
He and Cl 2The same He of shielding gas, the Cl of combination 2And O 2The gas of combination is compared and can be seen, all have shown all that by the photoconductive fiber that the preform of handling makes the loss that hydrogen causes increases in preceding a kind of combination of gases; And the photoconductive fiber that makes by the preform of handling in a kind of combination of gases in the back, the loss increase that its hydrogen causes is very slight.
Then, dehydration atmosphere is to use the latter, transparent glass gasification atmosphere to be to use above-mentioned gas (He and O 2Perhaps single He that uses), the preform that treatment temp T1 when changing dehydration respectively and transparent glass temperature T 2 are made regulation is made the preform wire drawing various photoconductive fiber samples then.
These photoconductive fibers have been measured the loss that is caused by hydrogen to be increased, and it the results are shown in Fig. 2.
Among Fig. 2, mark " * " expression has the loss that is caused by hydrogen to increase; Mark " zero " expression is not increased by the loss that hydrogen causes; Mark " ● " expression is not increased by the loss that hydrogen causes, but its initial loss is big; And mark " ▲ " expression OH absorption loss is big.
Among Fig. 2, T1=900 ℃ of occasion, cause the dehydration of chemical dehydration reaction and preform for optical fiber to become insufficient because temperature is low, therefore think that initial OH absorption loss is bigger, it is too low and uneven glass takes place form that solid mark " ● " is considered to second-order transition temperature.
On the other hand, to be considered to dehydration temperaturre too high in the zone that is marked with mark " * ". thereby produced independent closed pore (because chlorine enter).
In contrast, exist the zone of mark " zero " not cause variety of issue above-mentioned, for example inadequate dehydration, uneven glass are formed, the formation of independent closed pore etc., thereby show good result aspect the loss increase that causes in initial loss with by hydrogen.
See from these results, use Cl 2As the occasion of dehydrated air, its temperature T 1 and T2 are considered to preferably build within the zone that is surrounded by dotted line among Fig. 2.
Secondly, will be with regard to the present invention SOCl 2Replaced C l 2Experimental example as dehydrated air is illustrated.
When carrying out being shown in table 1 experiment identical, use SOCl with table 2 with those 2Replaced C l 2As dehydrated air, and the condition that dehydration and transparent glass chemical industry preface are carried out is shown in table 4 and table 5.
Figure 86100210_IMG6
The treatment process III is to dewater simultaneously and two operations of transparent glassization in the table 4; Treatment process IV in the table 5 then is to dewater respectively and transparent glass chemical industry preface; In these two kinds of processing, all use electric furnace shown in Figure 1.
In the table 5, the treatment temp when T1 represents to dewater; Treatment temp when T2 represents transparent glass.
As what can see from table 4 and table 5, the occasion of treatment process III with processing method IV relatively.The loss increase that the former hydrogen causes is bigger, has shown the tendency identical with The above results.
This result that the present invention shows is even use SOCl 2Also can expect to obtain same Cl as dehydrated air 2Same effect.
Narrate below with the experimental example of silicon fluoride as dehydrated air.
When the identical experiment carrying out and do, with silicon fluoride S i F with reference to table 1 and table 2 4Replaced C l 2As dehydrated air, dewater and the condition of transparent glass chemical industry preface is listed in table 6 and table 7.
Figure 86100210_IMG7
Figure 86100210_IMG8
Treatment process V in the table 6 is dewatered and transparent glass chemical industry preface simultaneously with above-mentioned same method; Treatment process VI in the table 7 is separately to dewater and transparent glass chemical industry preface; Each is handled and all uses electric furnace shown in Figure 1 to implement.
In the table 7, the treatment temp when T1 represents to dewater, T2 represents the treatment temp of transparent glassization.
Can see that from the result of table 6 and table 7 the treatment process V is compared with processing method VI, the loss increase that the former hydrogen causes is bigger.Shown the tendency identical with The above results.
Therefore be understandable that, use SiF in the inventive method 4As dehydrated air also is effective.But when using Si F 4During as dehydrated air, fluorine can be incorporated among the glass of processing, therefore, can see a kind of tendency, and promptly dehydration temperaturre T1 and transparent glass temperature T 2 reduce about 100 ℃ than the example of front.
The result draws from experimental example, is using SiF 4As the occasion of dehydrated air, temperature T 1 and T2 can be set among Fig. 4 in the dotted line institute area surrounded.
Among Fig. 4, identical among the implication of mark " * ", " zero ", " ● " and " ▲ " expression and Fig. 2.
In the above-mentioned experimental example, list Si F 4As dehydrated air, it is the representative of silicon fluoride, and other is as SiF 6, SiHF 3, SiH 2F 2, and SiH 3F is also effective, and CF 6Also effective.
But,, be necessary this muffle tube is taked antierosion measures if when the dehydrated air of using has erosion action to the silicon-dioxide muffle tube.
According to method of the present invention, then can provide following fibre-optic preform as mentioned above, promptly it has only little initial loss, and can not result from the peak that hydrogen that 1.52 micron wave strong points occur causes loss to increase.

Claims (8)

1, a kind of method of handling preform for optical fiber, with dehydration of porous silica soot matter preform and transparent glass processing, so that the transmission characteristics that the preform for optical fiber that obtains has in 1.2 to 1.6 microns of wavelength be 5 decibels/below the km, this method comprises:
Earlier preform is dewatered,
Then this preform carry out transparent glassization, so that this two procedure separately carries out,
Said dehydration procedure comprises: with helium He, oxygen O 2And dehydrated air is formed dehydration protection atmosphere; making treatment temp be set in the substantial dehydration of this porous soot matter preform, to begin temperature above but be lower than independent closed pore formation temperature; make this porous soot matter preform this treatment temp zone by above-mentioned dehydration protection atmosphere
Said transparent glass chemical industry preface comprises: with helium He, oxygen O 2Perhaps singly form transparent glass gasification atmosphere, treatment temp is set in more than the minimum transparent glass temperature, make preform this treatment temp zone by above-mentioned transparent glass gasification atmosphere after dehydration procedure with helium He.
2,, wherein dewater and the porous soot matter preform of transparent glass processing is produced by the VAD method according to the treatment process of the preform for optical fiber of claim 1.
3,, wherein dewater and the porous soot matter preform of transparent glass processing is produced by the OVPO method according to the treatment process of the preform for optical fiber of claim 1.
4, according to the treatment process of the preform for optical fiber of each claim of claim 1 to 3, wherein the treatment temp in the dehydration procedure is set in 900 ℃ to 1300 ℃.
5, according to the treatment process of the preform for optical fiber of each claim of claim 1 to 3, wherein the treatment temp in the transparent glass chemical industry preface is set in 1350 ° to 1650 ℃.
6, according to the treatment process of the preform for optical fiber of each claim of claim 1 to 4, wherein dehydrated air is a chlorine.
7, according to the treatment process of the preform for optical fiber of each claim of claim 1 to 4, wherein dehydrated air is a thionyl chloride.
8, according to the treatment process of the preform for optical fiber of each claim of claim 1 to 4, wherein dehydrated air is a silicon fluoride.
CN198686100210A 1985-01-14 1986-01-14 The treatment process of preform for optical fiber Pending CN86100210A (en)

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JP4535497B2 (en) * 2004-12-24 2010-09-01 信越石英株式会社 Method for producing synthetic silica glass with controlled OH group concentration
JP4789689B2 (en) * 2006-04-18 2011-10-12 信越化学工業株式会社 Low loss optical fiber preform manufacturing method
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CN106116121A (en) * 2016-08-31 2016-11-16 中国建筑材料科学研究总院 The preparation method of quartz glass and quartz glass

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GB8600792D0 (en) 1986-02-19

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