High homogeneity fluorine-doped quartz piece, method of making and optical fiber preform
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- WUHAN FIBERHOME RUITUO TECH CO LTD
- Filing Date
- 2023-12-20
- Publication Date
- 2026-06-26
AI Technical Summary
Existing technologies for fluorine-doped quartz sleeves suffer from problems such as low raw material utilization, poor uniformity of fluorine doping, and limited fluorine doping depth.
Based on the design parameters of the fluorine-doped quartz component, the required mass ratio of silica powder and fluoride powder is calculated. After mixing, the mixture is heated and melted, causing the fluoride powder to decompose and produce hydrogen fluoride, which reacts with the silica powder to achieve uniformity and depth of fluorine doping.
This improved raw material utilization, ensured the uniformity and depth of fluorine doping, reduced raw material waste, and enhanced product performance.
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Figure CN117735844B_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of optical fiber manufacturing technology, and in particular to a highly uniform fluorine-doped quartz component, its preparation method, and an optical fiber preform. Background Technology
[0002] Quartz, as a product of the optical fiber industry, has a long history of development and relatively high manufacturing technology. Traditional quartz sleeves are generally not required to have optical properties, but with the development of high-performance optical fibers, quartz sleeves are required to have certain properties in terms of refractive index, making them an important component in improving the optical performance of optical fibers.
[0003] Currently, the main methods for preparing fluorine-doped quartz sleeves are axial vapor deposition (VAD) or external chemical vapor deposition (OVD) to prepare quartz preforms, followed by fluorination through the introduction of fluorine-containing vapors during sintering. Both VAD and OVD methods have at least the following drawbacks:
[0004] Disadvantage 1: Because fluorine-containing vapors are introduced for doping and fluorination, some of the vapors will be discharged with the gas flow during the introduction process, resulting in a relatively low raw material utilization rate.
[0005] Disadvantage 2: Because fluorine-containing vapors are introduced during the sintering process, the fluorine-containing vapors need to gradually penetrate into the inside of the powder rod. This results in poor uniformity of fluorine doping along the radial direction of the powder rod, which affects the yield and product performance.
[0006] Disadvantage 3: Because fluorine-containing vapors are introduced during the sintering process, the fluorine-containing vapors need to gradually penetrate into the inside of the powder rod. This results in a limited fluorine doping depth along the radial direction of the powder rod, which affects the yield and product performance.
[0007] It is evident that the current production of fluorine-doped quartz sleeves suffers from problems such as low raw material utilization, poor uniformity, and limited fluorine doping depth. Summary of the Invention
[0008] This application provides a highly uniform fluorine-doped quartz component, a preparation method, and an optical fiber preform to solve the problems of poor uniformity of fluorine doping and low raw material utilization in related technologies.
[0009] In a first aspect, a method for preparing highly uniform fluorine-doped quartz parts is provided, comprising the following steps:
[0010] Based on the design relative refractive index difference of the fluorinated quartz component, the mass of the fluorinated quartz component, and the first mapping relationship of the relative refractive index difference of the fluorinated quartz component with respect to the mass of silica powder and the mass of fluoride powder, the required mass of silica powder and fluoride powder is obtained.
[0011] The silicon dioxide powder and the fluoride powder are mixed to obtain the precursor powder.
[0012] The precursor powder is heated and melted to react the hydrogen fluoride produced by the decomposition of the fluoride powder with the silicon dioxide powder, thereby obtaining a highly uniform fluorine-doped quartz component.
[0013] In some embodiments, the fluoride powder includes one or more of ammonium fluoride (NH4F), ammonium hexafluorosilicate (NH4)2SiF6, and ammonium hexafluorophosphate (NH4PF6).
[0014] In some embodiments, the heating and melting conditions include: a heating temperature of 1400°C to 1700°C and a heating time of 100 min to 200 min.
[0015] In some embodiments, based on the design relative refractive index difference of the fluorine-doped quartz component, the mass of the fluorine-doped quartz component, and a first mapping relationship between the relative refractive index difference of the fluorine-doped quartz component and the mass of silica powder and fluoride powder, the required mass of silica powder and fluoride powder is obtained, specifically including the following steps:
[0016] Based on the mass of the fluorine-doped quartz component, a second mapping relationship between the mass of the fluorine-doped quartz component and the mass of the silica powder and the fluoride powder is established;
[0017] Based on the design of the relative refractive index difference of the fluorine-doped quartz component, the first mapping relationship, and the second mapping relationship, the required mass of silica powder and fluoride powder is obtained.
[0018] In some embodiments, the first mapping relationship includes:
[0019]
[0020] Where Δ% is the relative refractive index difference of the fluorine-doped quartz component; m 氟化物粉末 For the mass of fluoride powder; m 二氧化硅粉末 The mass of silicon dioxide powder; a n-1 is the fitting constant.
[0021] In some embodiments, the second mapping relationship includes:
[0022] M = m 氟化物粉末 +m 二氧化硅粉末
[0023] Where M is the mass of the fluorine-doped quartz component; m 氟化物粉末 For the mass of fluoride powder; m 二氧化硅粉末 This refers to the mass of silicon dioxide powder.
[0024] In some embodiments, the fluorine content in the precursor powder is 5% to 20% by mass.
[0025] In some embodiments, heating and melting the precursor powder specifically includes:
[0026] The precursor powder is placed in a glass tube and heated to melt it, so that the fluorine-doped quartz part becomes a fluorine-doped quartz rod.
[0027] Alternatively, the precursor powder can be placed between two concentrically arranged glass tubes and heated to melt, so that the fluorinated quartz component becomes a fluorinated quartz tube.
[0028] Secondly, a highly uniform fluorine-doped quartz component is provided, which is prepared by any of the above-described methods for preparing highly uniform fluorine-doped quartz components.
[0029] Thirdly, an optical fiber preform is provided, comprising a highly uniform fluorine-doped quartz element prepared by any of the above-described methods for preparing highly uniform fluorine-doped quartz elements.
[0030] The beneficial effects of the technical solution provided in this application include:
[0031] This application provides a highly uniform fluorine-doped quartz component, its preparation method, and an optical fiber preform. Based on the required design parameters of the fluorine-doped quartz component, such as the design relative refractive index difference and mass, and using these two known parameters, combined with the first mapping relationship between the relative refractive index difference of the fluorine-doped quartz component and the mass of silica powder and fluoride powder, the required raw material mass for the fluorine-doped quartz component can be calculated, i.e., the required mass of silica powder and the required mass of fluoride powder. After mixing the required mass of silica powder and the required mass of fluoride powder, the precursor powder of the fluorine-doped quartz component is obtained. Then, the precursor powder is heated and melted. During the heating and melting process, the fluoride powder in the precursor powder undergoes a decomposition reaction under heating conditions, decomposing and producing hydrogen fluoride. The hydrogen fluoride undergoes a metathesis reaction with the silica powder in situ, thereby obtaining the fluorine-doped quartz component.
[0032] As can be seen, in this application, on the one hand, fluorine doping and product molding are carried out simultaneously; on the other hand, fluorine doping in this application is achieved through a two-step chemical reaction including decomposition reaction and metathesis reaction, and the chemical reaction between hydrogen fluoride and silicon dioxide powder is an in-situ reaction. It is only necessary to mix the required mass of silicon dioxide powder with the required mass of fluoride powder before heating and melting to ensure the uniformity and depth of fluorine doping. It is not necessary to use diffusion to achieve the uniformity and depth of fluorine doping.
[0033] Since the required mass of silica powder and fluoride powder is calculated based on the design parameters of the required fluorine-doped quartz component, only the required amount is used, thus reducing raw material waste and improving raw material utilization. Attached Figure Description
[0034] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0035] Figure 1 A flowchart illustrating the preparation method of highly uniform fluorine-doped quartz components provided in this application embodiment. Detailed Implementation
[0036] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.
[0037] See Figure 1 As shown in the embodiments of this application, a method for preparing highly uniform fluorine-doped quartz components is provided, which includes the following steps:
[0038] 101: Based on the design relative refractive index difference of fluorine-doped quartz components, the mass of fluorine-doped quartz components, and the first mapping relationship of the relative refractive index difference of fluorine-doped quartz components with respect to the mass of silica powder and the mass of fluoride powder, obtain the required mass of silica powder and fluoride powder.
[0039] 102: Mix the silicon dioxide powder and the fluoride powder to obtain a precursor powder;
[0040] 103: The precursor powder is heated and melted so that the hydrogen fluoride generated by the decomposition of the fluoride powder reacts with the silicon dioxide powder to obtain a highly uniform fluorine-doped quartz part.
[0041] The principle of the preparation method provided in this application is as follows:
[0042] Based on the design parameters of the required fluorinated quartz part, such as the design relative refractive index difference and mass, and using these two known parameters, combined with the first mapping relationship between the relative refractive index difference of the fluorinated quartz part and the mass of silica powder and fluoride powder, the required raw material mass of the fluorinated quartz part can be calculated, i.e., the required mass of silica powder and the required mass of fluoride powder. After mixing the required mass of silica powder and the required mass of fluoride powder, the precursor powder of the fluorinated quartz part can be obtained. Then, the precursor powder is heated and melted. During the heating and melting process, the fluoride powder in the precursor powder first undergoes a decomposition reaction under heating conditions, decomposing and producing hydrogen fluoride. The hydrogen fluoride undergoes a metathesis reaction with the silica powder in situ, thereby obtaining the fluorinated quartz part.
[0043] As can be seen, in this application, on the one hand, fluorine doping and product molding are carried out simultaneously; on the other hand, fluorine doping in this application is achieved through a two-step chemical reaction including decomposition reaction and metathesis reaction, and the chemical reaction between hydrogen fluoride and silicon dioxide powder is an in-situ reaction. It is only necessary to mix the required mass of silicon dioxide powder with the required mass of fluoride powder before heating and melting to ensure the uniformity and depth of fluorine doping. It is not necessary to use diffusion to achieve the uniformity and depth of fluorine doping.
[0044] Since the required mass of silica powder and fluoride powder is calculated based on the design parameters of the required fluorine-doped quartz component, only the required amount is used, thus reducing raw material waste and improving raw material utilization.
[0045] Since this application utilizes heating and melting to reduce raw material waste, improve raw material utilization, and ensure the uniformity and depth of fluorine doping, the raw materials can be in powder form, especially fluorides, which can form powdery substances and can also undergo thermal decomposition under heating to generate hydrogen fluoride.
[0046] As an example, the fluoride powder includes one or more of ammonium fluoride (NH4F), ammonium hexafluorosilicate (NH4)2SiF6, and ammonium hexafluorophosphate (NH4PF6).
[0047] It is understandable that the ammonia gas produced by the thermal decomposition of ammonium fluoride (NH4F), ammonium hexafluorosilicate (NH4)2SiF6, and ammonium hexafluorophosphate (NH4PF6) can be released during the melting process.
[0048] When ammonium hexafluorophosphate (NH4PF6) is used, not only fluorine doping can be achieved, but phosphorus doping can also be achieved simultaneously.
[0049] Understandably, in step 101, high-purity silica powder can be purchased directly or prepared in-house. Similarly, fluoride powder can also be purchased directly or prepared in-house.
[0050] For example, organosilicon or inorganic silicates are hydrolyzed and precipitated under weakly acidic conditions, then filtered, washed, and dried to obtain high-purity silica powder.
[0051] The heating and melting conditions are determined based on the physicochemical properties of the fluoride powder and the silicon dioxide powder, as well as the actual preparation requirements.
[0052] For example, the conditions for heating and melting include: a heating temperature of 1400℃~1700℃ and a heating time of 100min~200min.
[0053] Understandably, in step 101, based on the design relative refractive index difference of the fluorine-doped quartz component, the mass of the fluorine-doped quartz component, and the first mapping relationship between the relative refractive index difference of the fluorine-doped quartz component and the mass of the silica powder and the mass of the fluoride powder, the required mass of silica powder and fluoride powder is obtained, specifically including the following steps:
[0054] 201: Based on the mass of fluorine-doped quartz components, establish a second mapping relationship between the mass of fluorine-doped quartz components and the mass of silica powder and fluoride powder.
[0055] Specifically, the second mapping relationship includes:
[0056] M = m 氟化物粉末 +m 二氧化硅粉末
[0057] Where M is the mass of the fluorine-doped quartz component; m 氟化物粉末 For the mass of fluoride powder; m 二氧化硅粉末 This refers to the mass of silicon dioxide powder.
[0058] 202: Based on the design of the relative refractive index difference of the fluorine-doped quartz component, the first mapping relationship, and the second mapping relationship, the required mass of silica powder and fluoride powder is obtained.
[0059] Specifically, the first mapping relationship includes:
[0060]
[0061] Where Δ% is the relative refractive index difference of the fluorine-doped quartz component; m 氟化物粉末 For the mass of fluoride powder; m 二氧化硅粉末 The mass of silicon dioxide powder; a n-1 is the fitting constant.
[0062] Since the design relative refractive index difference and the mass of the fluorinated quartz component are known quantities, the design relative refractive index difference of the fluorinated quartz component can be substituted into the first mapping relationship mentioned above, and the mass of the fluorinated quartz component can be substituted into the second mapping relationship mentioned above. This allows us to construct a system of equations and calculate the required mass of silica powder and fluoride powder.
[0063] The first mapping relationship in step 202 can be obtained using the following method:
[0064] A certain amount of high-purity silica powder and fluoride powder were weighed repeatedly and mixed evenly to obtain precursor powder. The precursor powder was then heated and melted at a suitable temperature to prepare fluorine-doped quartz parts.
[0065] Measure the relative refractive index difference of each fluorine-doped quartz component;
[0066] Based on the relative refractive index difference of each fluorine-doped quartz component, the corresponding mass of silicon dioxide powder and the mass of fluoride powder, curve fitting is performed to obtain the above-mentioned first mapping relationship.
[0067] Furthermore, the power of the first mapping relationship fitted above can be determined according to actual needs.
[0068] For example, if we set n = 4, the first mapping relation we obtain is a cubic polynomial, as follows:
[0069]
[0070] It should be noted that the mass fraction of fluorine in the aforementioned precursor powder is 5% to 20%. This limitation is made to prevent the doping concentration from being too low if the mass fraction is too low, and to prevent the generation of too much gas during melting if the mass fraction is too high, which would lead to excessive pressure and could easily cause production safety accidents.
[0071] In step 103 above, heating and melting the precursor powder specifically includes:
[0072] The precursor powder is placed in a glass tube and heated to melt it, so that the fluorine-doped quartz part becomes a fluorine-doped quartz rod.
[0073] Alternatively, the precursor powder can be placed between two concentrically arranged glass tubes and heated to melt, so that the fluorinated quartz component becomes a fluorinated quartz tube.
[0074] In other words, the preparation method provided in this application can produce both solid fluorine-doped quartz rods and hollow fluorine-doped quartz tubes.
[0075] Furthermore, the relative refractive index difference of the fluorinated quartz parts obtained by melting can be measured online, and the real-time value of the relative refractive index difference can be fed back to the feeding system to monitor the relative refractive index difference in real time. If the relative refractive index difference exceeds the acceptable range, the precursor powder ratio can be adjusted to achieve high uniformity and consistency of the relative refractive index difference.
[0076] This application also provides a highly uniform fluorine-doped quartz component, which is prepared using the above-described method for preparing highly uniform fluorine-doped quartz components.
[0077] This application also provides an optical fiber preform, which includes a highly uniform fluorine-doped quartz component prepared by the above-described method for preparing highly uniform fluorine-doped quartz components.
[0078] In the description of this application, it should be noted that the terms "upper," "lower," etc., indicating the orientation or positional relationship are based on the orientation or positional relationship shown in the accompanying drawings, and are only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this application. Unless otherwise expressly specified and limited, the terms "installed," "connected," and "linked" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication between two elements. For those skilled in the art, the specific meaning of the above terms in this application can be understood according to the specific circumstances.
[0079] It should be noted that in this application, relational terms such as "first" and "second" are used merely to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.
[0080] The above description is merely a specific embodiment of this application, enabling those skilled in the art to understand or implement this application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of this application. Therefore, this application is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features claimed herein.
Claims
1. A method for preparing a highly uniform fluorine-doped quartz component, characterized in that, It includes the following steps: Based on the mass of the fluorine-doped quartz component, a second mapping relationship between the mass of the fluorine-doped quartz component and the mass of the silica powder and the fluoride powder is established; Based on the design of the relative refractive index difference of the fluorine-doped quartz component, the first mapping relationship, and the second mapping relationship, the required mass of silica powder and fluoride powder is obtained. The silicon dioxide powder and the fluoride powder are mixed to obtain the precursor powder. The precursor powder is heated and melted to react the hydrogen fluoride produced by the decomposition of the fluoride powder with the silicon dioxide powder, thereby obtaining a highly uniform fluorine-doped quartz part. The conditions for heating and melting include: a heating temperature of 1400℃~1700℃ and a heating time of 100min~200min; The first mapping relationship includes: in, The relative refractive index difference of fluorine-doped quartz components; For the mass of fluoride powder; The mass of silicon dioxide powder; Let n be the fitting constant and n be the power exponent. The second mapping relationship includes: in, For the quality of fluorine-doped quartz components; For the mass of fluoride powder; The mass of silicon dioxide powder; The mass fraction of fluorine in the precursor powder is 5% to 20%.
2. The method for preparing highly uniform fluorine-doped quartz components as described in claim 1, characterized in that: The fluoride powder includes one or more of ammonium fluoride (NH4F), ammonium hexafluorosilicate (NH4)2SiF6, and ammonium hexafluorophosphate (NH4PF6).
3. The method for preparing highly uniform fluorine-doped quartz components as described in claim 1, characterized in that, Heating and melting the precursor powder specifically includes: The precursor powder is placed in a glass tube and heated to melt it, so that the fluorine-doped quartz part becomes a fluorine-doped quartz rod. Alternatively, the precursor powder can be placed between two concentrically arranged glass tubes and heated to melt, so that the fluorinated quartz component becomes a fluorinated quartz tube.
4. A highly uniform fluorine-doped quartz component, characterized in that: It is prepared using the preparation method of highly uniform fluorine-doped quartz components as described in any one of claims 1 to 3.
5. An optical fiber preform, characterized in that: It includes highly uniform fluorine-doped quartz parts prepared by the preparation method of highly uniform fluorine-doped quartz parts as described in any one of claims 1 to 3.