本发明属于光纤技术领域，具体涉及一种光纤预制棒及其制备方法和应用。The present invention belongs to the technical field of optical fibers, and in particular relates to an optical fiber preform rod, a preparation method thereof, and an application thereof.
随着激光材料和激光技术的发展，研究人员发现通过向有源光纤中掺杂稀土元素，形成一定浓度的掺杂层，使光纤对某一波长的光具有显著的吸收和发射特性，能够实现更优异的光谱特性和光学效率。这种稀土掺杂有源光纤目前已广泛应用于光纤传感器中，作为光纤激光器中重要的增益介质，稀土掺杂有源光纤的性能优劣直接决定了激光器的性能，而预制棒是光纤的制备基础，预制棒的性能直接影响了光纤的性能，因此，如何制得性能优异的光纤预制棒是本领域的研究重点。With the development of laser materials and laser technology, researchers have discovered that by doping active optical fibers with rare earth elements to form a doping layer of a certain concentration, the optical fiber can have significant absorption and emission characteristics for light of a certain wavelength, achieving better spectral characteristics and optical efficiency. This rare earth-doped active optical fiber is currently widely used in optical fiber sensors. As an important gain medium in fiber lasers, the performance of rare earth-doped active optical fibers directly determines the performance of the laser. Preforms are the basis for the preparation of optical fibers, and the performance of preforms directly affects the performance of optical fibers. Therefore, how to produce optical fiber preforms with excellent performance is a research focus in this field.
目前，向有源光纤中掺杂稀土元素的方法包括气相法和液相法，气相法包括稀土氯化物气相沉积和稀土螯合物气相沉积；液相法包括管内稀土溶液浸泡法和管外稀土溶液浸泡法。其中气相法依赖于大型沉积设备，且掺杂浓度和均匀性难以控制，不利于光纤的性能提升；而液相法是先采用MCVD车床在沉积管内沉积光纤预制棒，然后将光纤预制棒浸泡在稀土溶液中，经氧化、干燥、烧结后得到稀土掺杂有源光纤预制棒，其中，管内稀土溶液浸泡法是指在沉积管内进行稀土溶液的浸泡，这种工艺需要使用氯气干燥，以去除溶液浸泡带来的羟基，从而实现预制棒的低损耗，但是长时间通入氯气会导致管道腐蚀，引起车床损坏；管外稀土溶液浸泡法是指在沉积管外进行稀土溶液的浸泡，该工艺在后续干燥步骤中不需要通入氯气，但是不使用氯气则无法将预制棒中的羟基完全去除，最终导致制备的光纤损耗增加，高损耗的光纤用于光纤激光器中则会进一步引起激光器功率下降。Currently, the methods for doping active optical fibers with rare earth elements include gas phase method and liquid phase method. The gas phase method includes rare earth chloride vapor deposition and rare earth chelate vapor deposition; the liquid phase method includes in-tube rare earth solution immersion method and out-tube rare earth solution immersion method. Among them, the gas phase method relies on large-scale deposition equipment, and the doping concentration and uniformity are difficult to control, which is not conducive to improving the performance of the optical fiber; the liquid phase method is to first use an MCVD lathe to deposit an optical fiber preform in a deposition tube, and then immerse the optical fiber preform in a rare earth solution. After oxidation, drying, and sintering, a rare earth-doped active optical fiber preform is obtained. Among them, the rare earth solution immersion method in the tube refers to immersing the rare earth solution in the deposition tube. This process requires the use of chlorine drying to remove the hydroxyl groups brought by the solution immersion, thereby achieving low loss of the preform. However, long-term introduction of chlorine will cause pipeline corrosion and damage to the lathe; the rare earth solution immersion method outside the tube refers to immersing the rare earth solution outside the deposition tube. This process does not require the introduction of chlorine in the subsequent drying step, but without the use of chlorine, the hydroxyl groups in the preform cannot be completely removed, which ultimately leads to increased loss of the prepared optical fiber. High-loss optical fiber used in fiber lasers will further cause a decrease in laser power.
因此，如何提供一种环保安全且能够有效降低光纤损耗的光纤预制棒的制备方法，是本领域亟待解决的技术问题。Therefore, how to provide a method for preparing an optical fiber preform that is environmentally friendly, safe, and can effectively reduce optical fiber loss is a technical problem that needs to be urgently solved in this field.
本发明提供一种光纤预制棒的制备方法，利用预氧化处理和氧化处理实现逐步氧化，并限定氧气的通入流量，能够实现稀土元素的充分氧化和最大限度地去除羟基，有助于降低光纤损耗，且该制备方法具有优异的环保性和安全性，适合大批量生产。The present invention provides a method for preparing an optical fiber preform rod, which utilizes pre-oxidation treatment and oxidation treatment to achieve gradual oxidation and limits the oxygen inlet flow rate, thereby achieving full oxidation of rare earth elements and maximal removal of hydroxyl groups, thereby helping to reduce optical fiber loss. In addition, the preparation method has excellent environmental protection and safety and is suitable for mass production.
本发明提供一种光纤预制棒，由于采用上述制备方法制得，利用该光纤预制棒制得的光纤具有低损耗的优势。The present invention provides an optical fiber preform rod. As it is manufactured by the above-mentioned manufacturing method, the optical fiber manufactured by using the optical fiber preform rod has the advantage of low loss.
本发明还提供一种光纤，由于采用上述光纤预制棒制备得到，该光纤具有低损耗的优势。The present invention also provides an optical fiber, which has the advantage of low loss due to being prepared by using the optical fiber preform rod.
本发明的第一方面，提供一种光纤预制棒的制备方法，包括以下步骤：A first aspect of the present invention provides a method for preparing an optical fiber preform, comprising the following steps:
将二氧化硅疏松体浸入含有稀土氯化物的溶液中，得到第一中间体；Immersing the silicon dioxide loose body in a solution containing rare earth chloride to obtain a first intermediate;
将第一中间体置于MCVD车床中，同时通入氧气和氦气以进行预氧化处理，继续通入氧气和氦气以进行氧化处理，得到第二中间体；其中，所述预氧化处理中氧气的通入流量为V1，所述氧化处理中氧气的通入流量为V2，满足V1：V2＝1：(5～10)；所述氧化处理的温度大于所述预氧化处理的温度；所述预氧化处理的压力大于所述氧化处理的压力；The first intermediate is placed in an MCVD lathe, and oxygen and helium are introduced simultaneously to perform a pre-oxidation treatment, and oxygen and helium are continued to be introduced to perform an oxidation treatment to obtain a second intermediate; wherein the oxygen introduction flow rate in the pre-oxidation treatment is V1, and the oxygen introduction flow rate in the oxidation treatment is V2, satisfying V1:V2=1:(5-10); the temperature of the oxidation treatment is greater than the temperature of the pre-oxidation treatment; and the pressure of the pre-oxidation treatment is greater than the pressure of the oxidation treatment;
将所述第二中间体依次进行烧结处理、熔缩处理后，得到光纤预制棒。The second intermediate is subjected to sintering treatment and melting treatment in sequence to obtain an optical fiber preform.
如上所述的制备方法，其中，所述预氧化处理中氦气的通入流量为V3，所述氧化处理中氦气的通入流量为V4，满足V3：V4＝(2～3)：1。In the preparation method as described above, the flow rate of helium in the pre-oxidation treatment is V3, and the flow rate of helium in the oxidation treatment is V4, satisfying V3:V4=(2-3):1.
如上所述的制备方法，其中，在所述预氧化处理中，氧气的通入流量为50～200sccm，氦气的通入流量为500～2000sccm；和/或，The preparation method as described above, wherein, in the pre-oxidation treatment, the flow rate of oxygen is 50-200 sccm, and the flow rate of helium is 500-2000 sccm; and/or,
在所述氧化处理中，氧气的通入流量为500～1000sccm，氦气的通入流量为500～1000sccm。During the oxidation treatment, the flow rate of oxygen gas is 500-1000 sccm, and the flow rate of helium gas is 500-1000 sccm.
如上所述的制备方法，其中，所述预氧化处理的温度为200～500℃，压力为0.9～1.5个大气压，时间为1.8～3.5h；和/或，The preparation method as described above, wherein the pre-oxidation treatment temperature is 200-500° C., the pressure is 0.9-1.5 atmospheres, and the time is 1.8-3.5 hours; and/or,
所述氧化处理的温度为400～800℃，压力为0.6～0.9个大气压，时间为1.5～2h。The oxidation treatment is performed at a temperature of 400 to 800° C., a pressure of 0.6 to 0.9 atmospheres, and a time of 1.5 to 2 hours.
如上所述的制备方法，其中，所述MCVD车床至少包括火焰喷灯、第一夹持单元和第二夹持单元；The preparation method as described above, wherein the MCVD lathe comprises at least a flame torch, a first clamping unit and a second clamping unit;
所述第一夹持单元和第二夹持单元沿自身轴线旋转，所述第一夹持单元和所述第二夹持单元用于相互配合夹设所述第一中间体；The first clamping unit and the second clamping unit rotate along their own axes, and the first clamping unit and the second clamping unit are used to cooperate with each other to clamp the first intermediate body;
所述火焰喷灯沿着所述第一中间体的轴向做往复移动，且所述火焰喷灯的喷射方向朝向所述第一中间体；The flame torch reciprocates along the axial direction of the first intermediate body, and the spraying direction of the flame torch is toward the first intermediate body;
在预氧化处理过程中，启动所述火焰喷灯使火焰喷灯沿着第一中间体的轴向发生第一往复移动；所述第一夹持单元和所述第二夹持单元带动所述第一中间体发生第一转动；During the pre-oxidation treatment, the flame burner is started to make a first reciprocating movement along the axial direction of the first intermediate body; the first clamping unit and the second clamping unit drive the first intermediate body to make a first rotation;
在氧化处理过程中，启动所述火焰喷灯使火焰喷灯沿着第一中间体的轴向发生第二往复移动；所述第一夹持单元和所述第二夹持单元带动所述第一中间体发生第二转动；During the oxidation treatment, the flame burner is started to make a second reciprocating movement along the axial direction of the first intermediate body; the first clamping unit and the second clamping unit drive the first intermediate body to make a second rotation;
所述第一转动的旋转速度为10～30rpm；所述第二转动的旋转速度为10～30rpm；The rotation speed of the first rotation is 10 to 30 rpm; the rotation speed of the second rotation is 10 to 30 rpm;
所述第一往复移动的速度为50～100mm/min；所述第二往复移动的速度为50～100mm/min。The speed of the first reciprocating movement is 50-100 mm/min; the speed of the second reciprocating movement is 50-100 mm/min.
如上所述的制备方法，其中，所述含有稀土氯化物的溶液中至少包含Y、Ce、Nd、Yd、Tm、Er中的至少一种元素；和/或，The preparation method as described above, wherein the solution containing rare earth chloride contains at least one element of Y, Ce, Nd, Yd, Tm, and Er; and/or,
所述含有稀土氯化物的溶液中的溶剂包括甲醇、乙醇、乙二醇中的至少一种。The solvent in the solution containing rare earth chloride includes at least one of methanol, ethanol and ethylene glycol.
如上所述的制备方法，其中，所述含有稀土氯化物的溶液中还包含Al、P中的至少一种元素。In the preparation method as described above, the solution containing rare earth chloride further contains at least one element selected from Al and P.
如上所述的制备方法，其中，所述烧结处理、熔缩处理均在含有氧气和氦气的混合气氛下进行；The preparation method as described above, wherein the sintering treatment and the melting treatment are both carried out in a mixed atmosphere containing oxygen and helium;
所述混合气氛中，氧气和氦气的体积比为1:(1～2)In the mixed atmosphere, the volume ratio of oxygen to helium is 1:(1-2)
本发明的第二方面，提供一种光纤预制棒，采用第一方面所述的制备方法制得。A second aspect of the present invention provides an optical fiber preform, which is produced by the production method described in the first aspect.
本发明的第三方面，提供一种光纤，采用第二方面所述的光纤预制棒制备得到。A third aspect of the present invention provides an optical fiber, which is prepared using the optical fiber preform described in the second aspect.
本发明的实施，至少具有以下有益效果：The implementation of the present invention has at least the following beneficial effects:
本发明提供的光纤预制棒的制备方法，利用液相法对二氧化硅疏松体进行稀土元素的掺杂，然后再经过预氧化处理和氧化处理实现逐步氧化，有效去除二氧化硅疏松体上的羟基，此外，通过限定预氧化处理和氧化处理过程中氧气的通入流量，能够实现稀土元素的充分氧化和最大限度地去除羟基，有助于降低光纤损耗，且该制备方法不使用氯气即可实现羟基的去处，具有优异的环保性和安全性，适合大批量生产。The method for preparing an optical fiber preform provided by the present invention utilizes a liquid phase method to dope a silica soot body with rare earth elements, and then performs a pre-oxidation treatment and an oxidation treatment to achieve gradual oxidation, thereby effectively removing hydroxyl groups on the silica soot body. In addition, by limiting the oxygen flow rate during the pre-oxidation treatment and the oxidation treatment, it is possible to fully oxidize the rare earth elements and remove hydroxyl groups to the maximum extent, thereby helping to reduce optical fiber loss. Moreover, the preparation method can remove hydroxyl groups without using chlorine gas, has excellent environmental protection and safety, and is suitable for mass production.
本发明提供的光纤预制棒，通过上述制备方法制得，利用该光纤预制棒制得的光纤具有低损耗的优势。The optical fiber preform provided by the present invention is manufactured by the above-mentioned manufacturing method, and the optical fiber manufactured by using the optical fiber preform has the advantage of low loss.
本发明还提供一种光纤，通过上述光纤预制棒拉丝成纤制得，该光纤具有低损耗的优势。The present invention also provides an optical fiber, which is obtained by drawing the optical fiber preform rod, and has the advantage of low loss.
为使本发明的目的、技术方案和优点更加清楚，下面将结合本发明的实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。To make the objectives, technical solutions, and advantages of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts shall fall within the scope of protection of the present invention.
本发明的第一方面，提供一种光纤预制棒的制备方法，包括以下步骤：将二氧化硅疏松体浸入含有稀土氯化物的溶液中，得到第一中间体；将稀土掺杂的二氧化硅疏松体置于MCVD车床中，同时通入氧气和氦气以进行预氧化处理，继续通入氧气和氦气以进行氧化处理，得到第二中间体；其中，预氧化处理中氧气的通入流量为V1，氧化处理中氧气的通入流量为V2，满足V1：V2＝1：(5～10)；氧化处理的温度大于预氧化处理的温度；预氧化处理的压力大于氧化处理的压力；将第二中间体依次进行烧结处理、熔缩处理后，得到光纤预制棒。A first aspect of the present invention provides a method for preparing an optical fiber preform, comprising the following steps: immersing a silica soot body in a solution containing a rare earth chloride to obtain a first intermediate; placing the rare earth-doped silica soot body in an MCVD lathe, and simultaneously introducing oxygen and helium to perform a pre-oxidation treatment, and continuing to introduce oxygen and helium to perform an oxidation treatment to obtain a second intermediate; wherein the oxygen flow rate during the pre-oxidation treatment is V1, and the oxygen flow rate during the oxidation treatment is V2, satisfying V1:V2=1:(5-10); the oxidation treatment temperature is greater than the pre-oxidation treatment temperature; the pre-oxidation treatment pressure is greater than the oxidation treatment pressure; and the second intermediate is sequentially sintered and melted to obtain an optical fiber preform.
本发明的二氧化硅疏松体是纳米二氧化硅颗粒的聚集形成的，本发明对二氧化硅疏松体的制备方法不做限定，例如以含硅化合物为原料，通过化学气相沉积制备上述二氧化硅疏松体。具体制备过程可包括以下步骤：将基管安装在MCVD车床上，向基管内在高温下通入SF6对基管进行抛光处理，待基管内壁光亮无杂质后，在基管内通入四氯化硅气体，依次沉积内包层和芯层，得到二氧化硅疏松体。The silica soot body of the present invention is formed by aggregation of nano-silica particles. The present invention does not limit the preparation method of the silica soot body. For example, the silica soot body can be prepared by chemical vapor deposition using a silicon-containing compound as a raw material. The specific preparation process may include the following steps: mounting a substrate tube on an MCVD lathe, polishing the substrate tube by passingSF6 into the substrate tube at high temperature, and then passing silicon tetrachloride gas into the substrate tube after the inner wall of the substrate tube is bright and free of impurities, sequentially depositing an inner cladding layer and a core layer to obtain the silica soot body.
其中，基管可以是本领域常规的沉积管，MCVD车床是本领域常规的用于制备光纤预制棒的装置，主要由玻璃车床、供料系统、温度测量和控制系统、管径测量和控制系统以及微机控制系统等组成。Among them, the substrate tube can be a conventional deposition tube in this field, and the MCVD lathe is a conventional device in this field for preparing optical fiber preform rods, which is mainly composed of a glass lathe, a feeding system, a temperature measurement and control system, a tube diameter measurement and control system, and a microcomputer control system.
本发明中，将基管安装在MCVD车床上，在基管内沉积得到二氧化硅疏松体，可直接将含有稀土氯化物的溶液注入沉积有二氧化硅疏松体的基管内，使得二氧化硅疏松体浸泡在含有稀土氯化物的溶液中，浸泡时间为0.5～2h，浸泡温度为30～45℃，去除多余的溶液，得到第一中间体。第一中间体实质上是掺杂有稀土元素的二氧化硅疏松体。In the present invention, a substrate tube is mounted on an MCVD lathe, and a silica soot body is deposited within the substrate tube. A solution containing a rare earth chloride is then directly injected into the substrate tube with the deposited silica soot body, allowing the silica soot body to be immersed in the rare earth chloride solution for 0.5 to 2 hours at a temperature of 30 to 45°C. Excess solution is then removed to obtain a first intermediate. The first intermediate is essentially a silica soot body doped with a rare earth element.
将含有稀土氯化物的溶液注入基管内，浸泡后，去除多余的溶液后，可直接将去除多余溶液后的基管安装在MCVD车床中，实施预氧化处理和氧化处理。A solution containing rare earth chloride is injected into the substrate tube. After soaking, excess solution is removed. The substrate tube after the excess solution is removed can be directly installed in an MCVD lathe to perform pre-oxidation treatment and oxidation treatment.
本发明中，同时通入氧气和氦气以进行预氧化处理和氧化处理时，由于气相本身具有良好的扩散性，能够与第一中间体充分接触，且分子量较小，氧气一方面能够氧化稀土元素，促进稀土元素的有效掺杂，另一方面能够去除表面的羟基，有效降低羟基对光纤的光学性能的负面影响。In the present invention, when oxygen and helium are introduced simultaneously for pre-oxidation treatment and oxidation treatment, since the gas phase itself has good diffusivity and can fully contact with the first intermediate, and has a small molecular weight, oxygen can, on the one hand, oxidize the rare earth elements and promote the effective doping of rare earth elements, and on the other hand, can remove the hydroxyl groups on the surface, effectively reducing the negative impact of the hydroxyl groups on the optical properties of the optical fiber.
通过设置预氧化处理和氧化处理，并逐步提升氧气的含量，有助于实现稀土元素的充分氧化，羟基的逐步氧化。此外，通过限定预氧化处理和氧化处理中氧气的通入流量比值，有利于最大限度地去除羟基。By implementing pre-oxidation and oxidation treatments and gradually increasing the oxygen content, it helps achieve full oxidation of rare earth elements and gradual oxidation of hydroxyl groups. In addition, by limiting the oxygen flow rate ratio between pre-oxidation and oxidation treatments, it helps to maximize the removal of hydroxyl groups.
预氧化处理中氧气的通入流量为V1，氧化处理中氧气的通入流量为V2，满足V1：V2＝1：(5～10)，例如1：5、1：6、1：7、1：8、1：9、1：10或其中的任意两者组成的范围。The oxygen flow rate in the pre-oxidation treatment is V1, and the oxygen flow rate in the oxidation treatment is V2, satisfying V1:V2=1:(5~10), for example, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10 or a range consisting of any two of them.
本发明中，氧化处理的温度大于预氧化处理的温度，预氧化处理的压力大于氧化处理的压力，有助于实现逐步氧化。In the present invention, the temperature of the oxidation treatment is higher than the temperature of the pre-oxidation treatment, and the pressure of the pre-oxidation treatment is higher than the pressure of the oxidation treatment, which is conducive to achieving gradual oxidation.
本发明中，烧结处理实质上促进中间体的玻璃化；熔缩处理实质上是促进中空的第二中间体形成实心的光纤预制棒。由于上述预氧化处理和氧化处理均是在MCVD车床上进行，经过预氧化处理和氧化处理之后，可直接在MCVD车床进行烧结处理和熔缩处理，有利于提高生产效率。In the present invention, the sintering process essentially promotes the vitrification of the intermediate body, while the melting process essentially promotes the formation of a solid optical fiber preform from the hollow second intermediate body. Because both the pre-oxidation and oxidation processes are performed on an MCVD lathe, the sintering and melting processes can be performed directly on the MCVD lathe after these processes, which improves production efficiency.
本发明可采用常规方法进行烧结处理和熔缩处理。例如可以使第二中间体升温至烧结温度，对第二中间体进行烧结处理，烧结处理结束后，再次升温进行熔缩处理，降温后得到光纤预制棒。烧结处理中，升温过程可以保持一定的升温速率，使第二中间体充分均匀受热后缓慢完成玻璃化过程，从而保证制得的光纤预制棒具有良好的光学均匀性。经烧结处理后，再次升温进行熔缩处理，经熔缩处理后，再以一定的降温速率降低温度，缓慢降温有助于改善光纤预制棒的内部应力缺陷，提升光纤预制棒的均匀性。The present invention can employ conventional methods for sintering and melting processes. For example, the second intermediate can be heated to a sintering temperature, sintered, and then heated again for melting. The optical fiber preform can then be cooled to obtain the optical fiber preform. During the sintering process, the heating process can be maintained at a constant heating rate, ensuring that the second intermediate is fully and evenly heated and then slowly undergoes the vitrification process, thereby ensuring that the optical fiber preform has good optical uniformity. After the sintering process, the temperature is again raised for melting. After the melting, the temperature is then cooled at a constant cooling rate. Slow cooling helps to improve internal stress defects in the optical fiber preform and enhance its uniformity.
本发明不限定氦气的通入流量，只要保证氧气和氦气同时通入即可。例如，在一些实施例中，预氧化处理中氦气的通入流量为V3，氧化处理中氦气的通入流量为V4，满足V3：V4＝(2～3)：1，例如2：1、2.5：1、3：1或其中的任意两者组成的范围。The present invention does not limit the flow rate of helium, as long as oxygen and helium are introduced simultaneously. For example, in some embodiments, the flow rate of helium during the pre-oxidation treatment is V3, and the flow rate of helium during the oxidation treatment is V4, satisfying V3:V4 = (2-3):1, such as 2:1, 2.5:1, 3:1, or any combination thereof.
本发明不限定氧气和氦气的具体通入流量，只要满足上述比例关系即可。例如，在一些实施例中，在预氧化处理中，氧气的通入流量为50～200sccm，例如50sccm、100sccm、150sccm、200sccm或其中的任意两者组成的范围，氦气的通入流量为500～2000sccm，例如500sccm、550sccm、1000sccm、1500sccm、2000sccm或其中的任意两者组成的范围；和/或，在氧化处理中，氧气的通入流量为500～1000sccm，例如500sccm、550sccm、1000sccm或其中的任意两者组成的范围，氦气的通入流量为500～1000sccm，例如500sccm、550sccm、1000sccm或其中的任意两者组成的范围。The present invention does not limit the specific flow rates of oxygen and helium, as long as the above-mentioned proportional relationship is satisfied. For example, in some embodiments, in the pre-oxidation treatment, the flow rate of oxygen is 50 to 200 sccm, for example, 50 sccm, 100 sccm, 150 sccm, 200 sccm, or a range consisting of any two thereof, and the flow rate of helium is 500 to 2000 sccm, for example, 500 sccm, 550 sccm, 1000 sccm, 1500 sccm, 2000 sccm, or a range consisting of any two thereof; and/or, in the oxidation treatment, the flow rate of oxygen is 500 to 1000 sccm, for example, 500 sccm, 550 sccm, 1000 sccm, or a range consisting of any two thereof, and the flow rate of helium is 500 to 1000 sccm, for example, 500 sccm, 550 sccm, 1000 sccm, or a range consisting of any two thereof.
本发明不限定预氧化处理和氧化处理的具体温度和压力，例如，在一些实施例中，预氧化处理的温度为200～500℃，例如200℃、250℃、300℃、350℃、400℃、450℃、500℃或其中的任意两者组成的范围，压力为0.9～1.5个大气压，例如0.9个大气压、1个大气压、1.2个大气压、1.5个大气压或其中的任意两者组成的范围，时间为1.8～3.5h；和/或，氧化处理的温度为400～800℃，例如400℃、450℃、500℃、550℃、600℃、650℃、700℃、750℃、800℃或其中的任意两者组成的范围，压力为0.6～0.9个大气压，例如0.6个大气压、0.7个大气压、0.8个大气压、0.9个大气压或其中的任意两者组成的范围，时间为1.5～2h。需要说明的是，上述温度和压力的选择需要满足：氧化处理温度大于预氧化处理温度，氧化处理压力小于预氧化处理压力。The present invention does not limit the specific temperature and pressure of the pre-oxidation treatment and the oxidation treatment. For example, in some embodiments, the temperature of the pre-oxidation treatment is 200-500° C., such as 200° C., 250° C., 300° C., 350° C., 400° C., 450° C., 500° C., or a range consisting of any two thereof, and the pressure is 0.9-1.5 atmospheres, such as 0.9 atmosphere, 1 atmosphere, 1.2 atmospheres, 1.5 atmospheres, or a range consisting of any two thereof. The time is 1.8 to 3.5 hours; and/or, the temperature of the oxidation treatment is 400 to 800°C, for example, 400°C, 450°C, 500°C, 550°C, 600°C, 650°C, 700°C, 750°C, 800°C, or a range consisting of any two thereof, and the pressure is 0.6 to 0.9 atmospheres, for example, 0.6 atmospheres, 0.7 atmospheres, 0.8 atmospheres, 0.9 atmospheres, or a range consisting of any two thereof, and the time is 1.5 to 2 hours. It should be noted that the selection of the above temperature and pressure needs to meet the following requirements: the oxidation treatment temperature is greater than the pre-oxidation treatment temperature, and the oxidation treatment pressure is less than the pre-oxidation treatment pressure.
本发明中，可利用加热单元对第一中间体进行加热，通过加热单元对第一中间体供温，能够保证预氧化处理和氧化处理的温度条件。In the present invention, the first intermediate body can be heated by a heating unit. By supplying temperature to the first intermediate body by the heating unit, the temperature conditions for the pre-oxidation treatment and the oxidation treatment can be ensured.
本发明不限定MCVD车床的具体类型，可以是本领域常规的MCVD车床。例如，在一些实施例中，MCVD车床至少包括火焰喷灯、第一夹持单元和第二夹持单元；第一夹持单元和第二夹持单元沿自身轴线旋转，第一夹持单元和第二夹持单元用于相互配合夹设第一中间体；火焰喷灯沿着第一中间体的轴向做往复移动，且火焰喷灯的喷射方向朝向第一中间体；在预氧化处理过程中，启动火焰喷灯使火焰喷灯沿着第一中间体的轴向发生第一往复移动；第一夹持单元和第二夹持单元带动第一中间体发生第一转动；在氧化处理过程中，启动火焰喷灯使火焰喷灯沿着第一中间体的轴向发生第二往复移动；第一夹持单元和第二夹持单元带动第一中间体发生第二转动。The present invention does not limit the specific type of MCVD lathe, which can be a conventional MCVD lathe in the field. For example, in some embodiments, the MCVD lathe includes at least a flame burner, a first clamping unit, and a second clamping unit; the first clamping unit and the second clamping unit rotate along their own axes, and the first clamping unit and the second clamping unit are used to cooperate with each other to clamp the first intermediate; the flame burner reciprocates along the axial direction of the first intermediate, and the spray direction of the flame burner is toward the first intermediate; during the pre-oxidation treatment process, the flame burner is started to make a first reciprocating movement along the axial direction of the first intermediate; the first clamping unit and the second clamping unit drive the first intermediate to make a first rotation; during the oxidation treatment process, the flame burner is started to make a second reciprocating movement along the axial direction of the first intermediate; the first clamping unit and the second clamping unit drive the first intermediate to make a second rotation.
其中，第一中间体、第一夹持单元、第二夹持单元是同轴延伸。伴随着第一夹持单元和第二夹持单元沿自身轴线旋转，第一中间体能够沿自身轴线旋转。The first intermediate body, the first clamping unit and the second clamping unit are coaxially extended. As the first clamping unit and the second clamping unit rotate along their own axes, the first intermediate body can rotate along its own axis.
火焰喷灯用于将火焰喷射至第一中间体上以使第一中间体的温度达到预氧化处理和氧化处理的温度。在预氧化处理和氧化处理的温度过程中，火焰喷灯的喷射方向朝向第一中间体，且火焰喷灯沿着第一中间体的轴向做往复移动。The flame torch is used to spray flame onto the first intermediate body to bring the temperature of the first intermediate body to the temperature required for the pre-oxidation treatment and the oxidation treatment. During the pre-oxidation treatment and the oxidation treatment, the flame torch sprays toward the first intermediate body and reciprocates along the axial direction of the first intermediate body.
其中，第一转动的旋转速度为10～30rpm，例如10rpm、15rpm、20rpm、25rpm、30rpm或其中的任意两者组成的范围；第二转动的旋转速度为10～30rpm，例如10rpm、15rpm、20rpm、25rpm、30rpm或其中的任意两者组成的范围；第一往复移动的速度为50～100mm/min，例如50mm/min、60mm/min、70mm/min、80mm/min、90mm/min、100mm/min或其中的任意两者组成的范围；第二往复移动的速度为50～100mm/min，例如50mm/min、60mm/min、70mm/min、80mm/min、90mm/min、100mm/min或其中的任意两者组成的范围，第一往复移动的次数为5～20次，第二往复移动的次数为5～20次。wherein, the rotation speed of the first rotation is 10 to 30 rpm, for example, 10 rpm, 15 rpm, 20 rpm, 25 rpm, 30 rpm or a range consisting of any two thereof; the rotation speed of the second rotation is 10 to 30 rpm, for example, 10 rpm, 15 rpm, 20 rpm, 25 rpm, 30 rpm or a range consisting of any two thereof; the speed of the first reciprocating movement is 50 to 100 mm/min, for example, 50 mm/min, 60 mm/min, 70 mm/min, 80 mm/min, 90 mm/min, 100 mm/min or a range consisting of any two thereof; the speed of the second reciprocating movement is 50 to 100 mm/min, for example, 50 mm/min, 60 mm/min, 70 mm/min, 80 mm/min, 90 mm/min, 100 mm/min or a range consisting of any two thereof, the number of the first reciprocating movement is 5 to 20 times, and the number of the second reciprocating movement is 5 to 20 times.
其中，第一往复移动和第二往复移动均是指火焰喷灯沿着第一中间体的轴向方向的一端至另一端，再从第一中间体的轴向方向的另一端至一端的往复移动；第一往复移动的距离是第一中间体自身纵向长度的2倍，第一转动和第二转动均是指第一中间体沿着自身轴线旋转。Among them, the first reciprocating movement and the second reciprocating movement both refer to the reciprocating movement of the flame torch along the axial direction of one end of the first intermediate body to the other end, and then from the other end to one end of the axial direction of the first intermediate body; the distance of the first reciprocating movement is twice the longitudinal length of the first intermediate body itself, and the first rotation and the second rotation both refer to the rotation of the first intermediate body along its own axis.
以第一往复移动为例，火焰喷灯沿着第一中间体的轴向方向的一端至另一端，再从第一中间体的轴向方向的另一端至一端为1次往复移动。Taking the first reciprocating movement as an example, the flame torch moves from one end to the other end of the first intermediate body in the axial direction, and then from the other end to one end of the first intermediate body in the axial direction, which is one reciprocating movement.
本发明中，第一夹持单元和第二夹持单元可通过卡盘调节旋转速度。In the present invention, the first clamping unit and the second clamping unit can adjust the rotation speed through the chuck.
其中，在预氧化处理过程中，火焰喷灯的H2流量为25～50slm；在氧化处理过程中，火焰喷灯的H2流量为35～55slm，其中，slm表示标准状况下(0℃，1atm)升每分钟。During the pre-oxidation process, the H2 flow rate of the flame burner is 25 to 50 slm; during the oxidation process, the H2 flow rate of the flame burner is 35 to 55 slm, where slm represents liters per minute under standard conditions (0°C, 1 atm).
本发明不限定含有稀土氯化物的溶液的具体类型，只要含有稀土氯化物即可，例如，在一些实施例中，含有稀土氯化物的溶液中至少包含Y、Ce、Nd、Yd、Tm、Er中的至少一种元素；和/或，含有稀土氯化物的溶液中的溶剂包括甲醇、乙醇、乙二醇中的至少一种。The present invention is not limited to the specific type of solution containing rare earth chloride, as long as it contains rare earth chloride. For example, in some embodiments, the solution containing rare earth chloride contains at least one element of Y, Ce, Nd, Yd, Tm, and Er; and/or, the solvent in the solution containing rare earth chloride includes at least one of methanol, ethanol, and ethylene glycol.
在一种可能的实施方式中，含有稀土氯化物的溶液中还包含Al、P中的至少一种元素。In a possible embodiment, the solution containing rare earth chloride further contains at least one element of Al and P.
本发明不限定烧结处理和熔缩处理的具体实施方式，可以采用本领域常规的烧结处理和熔缩处理方法实施。在一些实施例中，烧结处理、熔缩处理均在含有氧气和氦气的混合气氛下进行；混合气氛中，氧气和氦气的体积比为1:(1～2)。The present invention does not limit the specific implementation methods of the sintering and melting treatments, and conventional sintering and melting treatment methods in the art can be used. In some embodiments, the sintering and melting treatments are both performed in a mixed atmosphere containing oxygen and helium; the volume ratio of oxygen to helium in the mixed atmosphere is 1:(1-2).
本发明的第二方面，提供一种光纤预制棒，采用第一方面提供的制备方法制得。由于采用上述制备方法制得，利用该光纤预制棒制得的光纤具有低损耗的优势。The second aspect of the present invention provides an optical fiber preform, which is produced by the production method provided in the first aspect. Due to the production method, the optical fiber produced by using the optical fiber preform has the advantage of low loss.
本发明的第三方面，提供一种光纤，由于采用上述光纤预制棒制备得到，该光纤具有低损耗的优势。本发明的光纤可通过对光纤预制棒实施本领域常规的拉丝成纤方法制得。The third aspect of the present invention provides an optical fiber, which has the advantage of low loss due to being prepared using the optical fiber preform. The optical fiber of the present invention can be prepared by subjecting the optical fiber preform to conventional fiber drawing methods in the art.
下面通过具体实施例和对比例对本发明作进一步的说明。如无特别说明，下述所使用到的试剂、材料以及仪器均为常规试剂、常规材料以及常规仪器，均可商购获得，所涉及的试剂、材料也可通过常规合成方法合成获得。The present invention is further described below by way of specific examples and comparative examples. Unless otherwise specified, the reagents, materials, and instruments used below are all conventional reagents, materials, and instruments, all of which are commercially available, and the reagents and materials involved can also be synthesized by conventional synthesis methods.
实施例1Example 1
(1)将基管安装在MCVD车床上，在加热温度为1600℃条件下，向基管内通入SF6进行预加热抛光；在加热温度为1400℃，以通入流量为3g/min向基管内通入SiCl4，在基管内沉积二氧化硅疏松体；(1) The substrate tube was mounted on an MCVD lathe. SF6 was introduced into the substrate tube at a heating temperature of 1600°C for preheating and polishing. SiCl4 was introduced into the substrate tube at a heating temperature of 1400°C at a flow rate of 3 g/min to deposit a loose silica body in the substrate tube.
(2)向沉积有二氧化硅疏松体的基管内通入含有氯化镱、氯化铝、磷酸的甲醇溶液中，浸泡时间为0.5h，去除多余的溶液后，得到第一中间体；(2) introducing a methanol solution containing ytterbium chloride, aluminum chloride, and phosphoric acid into the substrate tube on which the silica loose body is deposited for 0.5 h, and removing excess solution to obtain a first intermediate;
(3)将盛放有第一中间体的基管重新安装在MCVD车床上，同时通入氧气和氦气以进行预氧化处理；预氧化处理中，氧气流量为50sccm，氦气流量为1000sccm，基管内压力为1.1个大气压，火焰喷灯的往复移动速度为100mm/min；卡盘的转速为30rpm，加热温度为300℃，预氧化处理的时间为2h；(3) The substrate tube containing the first intermediate was reinstalled on the MCVD lathe, and oxygen and helium were introduced simultaneously for pre-oxidation treatment; during the pre-oxidation treatment, the oxygen flow rate was 50 sccm, the helium flow rate was 1000 sccm, the pressure in the substrate tube was 1.1 atmospheres, the reciprocating speed of the flame torch was 100 mm/min, the chuck speed was 30 rpm, the heating temperature was 300° C., and the pre-oxidation treatment time was 2 h;
(4)继续通入氧气和氦气以进行氧化处理，得到第二中间体；氧化处理中，氧气流量为500sccm，氦气流量为500sccm，管内压力为0.7个大气压，火焰喷灯的往复移动速度为100mm/min，加热温度为400℃，氧化处理的时间为1.5h；(4) continuing to introduce oxygen and helium to carry out oxidation treatment to obtain a second intermediate; during the oxidation treatment, the oxygen flow rate is 500 sccm, the helium flow rate is 500 sccm, the pressure in the tube is 0.7 atmospheres, the reciprocating speed of the flame burner is 100 mm/min, the heating temperature is 400°C, and the oxidation treatment time is 1.5 h;
(5)将第二中间体进行烧结处理和熔缩处理，烧结温度为2000℃，熔缩温度为2150℃，得到实心的光纤预制棒。(5) The second intermediate is subjected to sintering and melting treatments, with the sintering temperature being 2000° C. and the melting temperature being 2150° C., to obtain a solid optical fiber preform.
实施例2Example 2
(1)将基管安装在MCVD车床上，在加热温度为1700℃的条件下，向基管内通入SF6进行预加热抛光；在加热温度为1500℃的条件下，以通入流量为2.6g/min向基管内通入SiCl4，在基管内沉积二氧化硅疏松体；(1) The substrate tube was mounted on an MCVD lathe, and SF6 was introduced into the substrate tube for preheating and polishing at a heating temperature of 1700°C. SiCl4 was introduced into the substrate tube at a flow rate of 2.6 g/min at a heating temperature of 1500°C to deposit a loose silica body in the substrate tube.
(2)向沉积有二氧化硅疏松体的基管内通入含有氯化铒、氯化铝的乙醇溶液中，浸泡时间为1h，去除多余的溶液后，得到第一中间体；(2) introducing an ethanol solution containing erbium chloride and aluminum chloride into the substrate tube on which the silica loose body is deposited for 1 hour, and removing excess solution to obtain a first intermediate;
(3)将盛放有第一中间体的基管重新安装在MCVD车床上，同时通入氧气和氦气以进行预氧化处理；预氧化处理中，氧气流量为100sccm，氦气流量为1500sccm，基管内压力为1.3个大气压，火焰喷灯的往复移动速度为70mm/min；卡盘的转速为15rpm，加热温度为500℃，预氧化处理的时间为1.8h；(3) The substrate tube containing the first intermediate was reinstalled on the MCVD lathe, and oxygen and helium were introduced simultaneously for pre-oxidation treatment; during the pre-oxidation treatment, the oxygen flow rate was 100 sccm, the helium flow rate was 1500 sccm, the pressure in the substrate tube was 1.3 atmospheres, the reciprocating speed of the flame torch was 70 mm/min, the chuck speed was 15 rpm, the heating temperature was 500° C., and the pre-oxidation treatment time was 1.8 h;
(4)继续通入氧气和氦气以进行氧化处理，得到第二中间体；氧化处理中，氧气流量为700sccm，氦气流量为700sccm，管内压力为0.9个大气压，火焰喷灯的往复移动速度为70mm/min，加热温度为700℃，氧化处理的时间为2h；(4) continuing to introduce oxygen and helium to carry out oxidation treatment to obtain a second intermediate; during the oxidation treatment, the oxygen flow rate is 700 sccm, the helium flow rate is 700 sccm, the pressure in the tube is 0.9 atmospheres, the reciprocating speed of the flame burner is 70 mm/min, the heating temperature is 700°C, and the oxidation treatment time is 2 h;
(5)将第二中间体进行烧结处理和熔缩处理，烧结温度为1950℃，熔缩温度为2200℃，得到实心的光纤预制棒。(5) The second intermediate is subjected to sintering and melting treatments, with the sintering temperature being 1950° C. and the melting temperature being 2200° C., to obtain a solid optical fiber preform.
实施例3Example 3
(1)将基管安装在MCVD车床上，在加热温度为1800℃的条件下，向基管内通入SF6进行预加热抛光；在加热温度为1600℃的条件下，以通入流量为3.3g/min向基管内通入SiCl4，在基管内沉积二氧化硅疏松体；(1) The substrate tube was mounted on an MCVD lathe, and SF6 was introduced into the substrate tube at a heating temperature of 1800°C for preheating and polishing. SiCl4 was introduced into the substrate tube at a flow rate of 3.3 g/min at a heating temperature of 1600°C to deposit a loose silica body in the substrate tube.
(2)向沉积有二氧化硅疏松体的基管内通入含有氯化铥、氯化铝的乙醇溶液中，浸泡时间为2h，去除多余的溶液后，得到第一中间体；(2) introducing an ethanol solution containing thulium chloride and aluminum chloride into the substrate tube on which the silica loose body is deposited for 2 hours, and removing excess solution to obtain a first intermediate;
(3)将盛放有第一中间体的基管重新安装在MCVD车床上，同时通入氧气和氦气以进行预氧化处理；预氧化处理中，氧气流量为200sccm，氦气流量为2000sccm，基管内压力为1.5个大气压，火焰喷灯的往复移动速度为50mm/min；卡盘的转速为10rpm，加热温度为250℃，预氧化处理的时间为3.5h；(3) The substrate tube containing the first intermediate was reinstalled on the MCVD lathe, and oxygen and helium were introduced simultaneously for pre-oxidation treatment; during the pre-oxidation treatment, the oxygen flow rate was 200 sccm, the helium flow rate was 2000 sccm, the pressure in the substrate tube was 1.5 atmospheres, the reciprocating speed of the flame torch was 50 mm/min, the chuck speed was 10 rpm, the heating temperature was 250° C., and the pre-oxidation treatment time was 3.5 h;
(4)继续通入氧气和氦气以进行氧化处理，得到第二中间体；其中，氧气流量为1000sccm，氦气流量为1000sccm，管内压力为0.6个大气压，火焰喷灯的往复移动速度为50mm/min，加热温度为400℃，氧化处理的时间为1.5h；(4) continuing to introduce oxygen and helium to perform oxidation treatment to obtain a second intermediate; wherein the oxygen flow rate is 1000 sccm, the helium flow rate is 1000 sccm, the pressure in the tube is 0.6 atmospheres, the reciprocating speed of the flame burner is 50 mm/min, the heating temperature is 400°C, and the oxidation treatment time is 1.5 h;
(5)将第二中间体进行烧结处理和熔缩处理，烧结温度为2050℃，熔缩温度为2280℃，得到实心的光纤预制棒。(5) The second intermediate is subjected to sintering and melting treatments, with the sintering temperature being 2050° C. and the melting temperature being 2280° C., to obtain a solid optical fiber preform.
对比例1(管外法制备的有源光纤)Comparative Example 1 (Active Optical Fiber Prepared by the Out-of-Tube Method)
采用VAD工艺沉积制备一支外径为150mm，长度为754mm，密度为2.1g/cm3纯SiO2粉棒，在1400℃烧结炉中预烧结，得到一支75mm，长度526mm，密度2.72g/cm3纯SiO2粉棒；称取氯化铝、氯化镱、磷酸的乙醇溶液，预烧结后的粉棒在上述溶液中浸泡48h，然后将粉棒缓慢提出。A pureSiO2 powder rod with an outer diameter of 150 mm, a length of 754 mm, and a density of 2.1 g/cm3 was prepared by VAD deposition. It was pre-sintered in a sintering furnace at 1400°C to obtain a pureSiO2 powder rod with an outer diameter of 75 mm, a length of 526 mm, and a density of 2.72 g/cm3. An ethanol solution of aluminum chloride, ytterbium chloride, and phosphoric acid was weighed, and the pre-sintered powder rod was soaked in the above solution for 48 hours, and then the powder rod was slowly taken out.
提出后的粉棒置于-40℃，2.4个标准大气压的干燥罐中干燥。然后在烧结炉中将粉棒熔缩成外径51mm透明实心预制棒，即为稀土掺杂光纤预制棒。The extracted powder rod is placed in a drying jar at -40°C and 2.4 standard atmospheres to dry. It is then melted and sintered in a sintering furnace to form a transparent solid preform rod with an outer diameter of 51 mm, which is the rare earth-doped optical fiber preform rod.
对比例2Comparative Example 2
(1)将基管安装在MCVD车床上，在加热温度为1550℃条件下，向基管内通入SF6进行预加热抛光；在加热温度为1500℃时，向基管内通入流量为2.3g/min的SiCl4，同时通入流量为50sccm的Cl2，在基管内沉积二氧化硅疏松体；(1) The substrate tube was mounted on an MCVD lathe. SF6 was introduced into the substrate tube for preheating and polishing at a heating temperature of 1550°C. When the heating temperature reached 1500°C, SiCl4 at a flow rate of 2.3 g/min and Cl2 at a flow rate of 50 sccm were introduced into the substrate tube to deposit a loose silica body in the substrate tube.
(2)向沉积有二氧化硅疏松体的基管内通入含有氯化镱、氯化铝、磷酸的乙醇溶液中，浸泡时间为0.6h，温度为35℃，去除多余的溶液后，得到第一中间体；(2) introducing an ethanol solution containing ytterbium chloride, aluminum chloride, and phosphoric acid into the substrate tube on which the silica loose body is deposited, the immersion time is 0.6 h, the temperature is 35° C., and after removing the excess solution, a first intermediate is obtained;
(3)将盛放有第一中间体的基管重新安装在MCVD车床上，同时通入氧气和氦气以进行预氧化处理；预氧化处理中，氧气流量为1000sccm；氦气流量为1000sccm，基管内压力为1.1个大气压，火焰喷灯的往复移动速度为100mm/min；卡盘的转速为60rpm，加热温度为400℃，预氧化处理的时间为3h；(4)继续通入氧气和氦气以进行氧化处理，得到第二中间体；干燥处理中，氧气流量为500sccm，氦气流量为1500sccm，氯气流量为500sccm，管内压力为1.2个大气压，火焰喷灯的往复移动速度为120mm/min，卡盘转速为56rpm，加热温度为400℃，氧化处理的时间为6h；(3) The substrate tube containing the first intermediate is reinstalled on the MCVD lathe, and oxygen and helium are introduced at the same time for pre-oxidation treatment; during the pre-oxidation treatment, the oxygen flow rate is 1000 sccm; the helium flow rate is 1000 sccm, the pressure in the substrate tube is 1.1 atmospheres, the reciprocating speed of the flame torch is 100 mm/min; the rotation speed of the chuck is 60 rpm, the heating temperature is 400°C, and the pre-oxidation treatment time is 3 hours; (4) Oxygen and helium are continued to be introduced for oxidation treatment to obtain the second intermediate; during the drying treatment, the oxygen flow rate is 500 sccm, the helium flow rate is 1500 sccm, the chlorine flow rate is 500 sccm, the pressure in the tube is 1.2 atmospheres, the reciprocating speed of the flame torch is 120 mm/min, the rotation speed of the chuck is 56 rpm, the heating temperature is 400°C, and the oxidation treatment time is 6 hours;
(5)将第二中间体进行烧结处理和熔缩处理，烧结温度为2000℃，熔缩温度为2300℃，得到实心的光纤预制棒。(5) The second intermediate is subjected to sintering and melting treatments, with the sintering temperature being 2000° C. and the melting temperature being 2300° C., to obtain a solid optical fiber preform.
对比例3Comparative Example 3
(1)将基管安装在MCVD车床上，在加热温度为1550℃条件下，向基管内通入SF6进行预加热抛光；在加热温度为1500℃，以通入流量为2.6g/min向基管内通入SiCl4，在基管内沉积二氧化硅疏松体；(1) The substrate tube was mounted on an MCVD lathe, and SF6 was introduced into the substrate tube at a heating temperature of 1550°C for preheating and polishing. At a heating temperature of 1500°C, SiCl4 was introduced into the substrate tube at a flow rate of 2.6 g/min to deposit a loose silica body in the substrate tube.
(2)向沉积有二氧化硅疏松体的基管内通入含有氯化镱、氯化铝、磷酸的水溶液中，浸泡时间为0.4h，温度为25℃，去除多余的溶液后，得到第一中间体；(2) introducing an aqueous solution containing ytterbium chloride, aluminum chloride, and phosphoric acid into the substrate tube on which the silica loose body is deposited, the immersion time is 0.4 h, the temperature is 25° C., and after removing the excess solution, a first intermediate is obtained;
(3)将盛放有第一中间体的基管重新安装在MCVD车床上，同时通入氧气和氦气以进行预氧化处理；其中氧化流量为250sccm；氦气流量为450sccm，基管内压力为0.8个大气压，火焰喷灯的往复移动速度为42mm/min；卡盘的转速为60rpm，加热温度为600℃，预氧化处理的时间为4h；(3) The substrate tube containing the first intermediate was reinstalled on the MCVD lathe, and oxygen and helium were introduced simultaneously for pre-oxidation treatment; wherein the oxidation flow rate was 250 sccm; the helium flow rate was 450 sccm, the pressure in the substrate tube was 0.8 atmospheres, the reciprocating speed of the flame torch was 42 mm/min; the chuck rotation speed was 60 rpm, the heating temperature was 600°C, and the pre-oxidation treatment time was 4 h;
(4)继续通入氧气和氦气以进行氧化处理，得到第二中间体；其中，氧气流量为1000sccm，氦气流量为450sccm，管内压力为1.2个大气压，火焰喷灯的往复移动速度为120mm/min，卡盘转速为56rpm，加热温度为400℃，氧化处理时间为1h；(4) continuing to introduce oxygen and helium to perform oxidation treatment to obtain a second intermediate; wherein the oxygen flow rate is 1000 sccm, the helium flow rate is 450 sccm, the pressure in the tube is 1.2 atmospheres, the reciprocating speed of the flame burner is 120 mm/min, the chuck speed is 56 rpm, the heating temperature is 400°C, and the oxidation treatment time is 1 h;
(5)将第二中间体进行烧结处理和熔缩处理，烧结温度为1900℃，熔缩温度为2300℃，得到实心的光纤预制棒。(5) The second intermediate is subjected to sintering and melting treatments, with the sintering temperature being 1900° C. and the melting temperature being 2300° C., to obtain a solid optical fiber preform.
试验例Test example
将上述光纤预制棒在2000℃的拉丝温度及15mm/min的拉丝速度下直接拉丝，得到光纤；采用截断阀测试光纤在波长为1200nm的损耗、以及波长为1380nm的损耗，测试结果见表1。The optical fiber preform was directly drawn at a drawing temperature of 2000°C and a drawing speed of 15 mm/min to obtain an optical fiber. The optical fiber loss at a wavelength of 1200 nm and a wavelength of 1380 nm were tested using a cutoff valve. The test results are shown in Table 1.
表1
Table 1
根据表1可知，本发明利用预氧化处理和氧化处理实现逐步氧化，并限定氧气的通入流量，能够实现稀土元素的充分氧化和最大限度地去除羟基，有助于降低光纤损耗，且该制备方法具有优异的环保性和安全性，适合大批量生产。As can be seen from Table 1, the present invention utilizes pre-oxidation and oxidation treatments to achieve gradual oxidation, and limits the oxygen flow rate, which can achieve full oxidation of rare earth elements and maximize the removal of hydroxyl groups, thereby helping to reduce optical fiber loss. In addition, this preparation method has excellent environmental protection and safety, and is suitable for mass production.
利用实施例1的制备方法制得光纤预制棒近50根后，MCVD车床的进气管道保持整洁并无明显锈蚀，而对比例2的含氯工艺在制备50根光纤预制棒后，MCVD车床的进气管道锈蚀严重，为此需定期更换进气管道。After nearly 50 optical fiber preforms were produced using the preparation method of Example 1, the air intake duct of the MCVD lathe remained clean and had no obvious rust. However, after 50 optical fiber preforms were produced using the chlorine-containing process of Comparative Example 2, the air intake duct of the MCVD lathe was severely corroded, and the air intake duct needed to be replaced regularly.
以上详细描述了本发明的较佳具体实施例以及试验验证。应当理解，本领域的普通技术无需创造性劳动就可以根据本发明的构思作出诸多修改和变化。因此，凡本技术领域中技术人员依本发明的构思在现有技术的基础上通过逻辑分析、推理或者有限的实验可以得到的技术方案，皆应在本发明的保护范围内。The above describes in detail the preferred embodiments of the present invention and their experimental verification. It should be understood that a person skilled in the art can make numerous modifications and variations based on the concepts of the present invention without inventive effort. Therefore, any technical solution that can be derived by a person skilled in the art through logical analysis, reasoning, or limited experimentation based on the concepts of the present invention and the prior art shall be within the scope of protection of the present invention.
| Application Number | Priority Date | Filing Date | Title |
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| CN202410163945.9ACN117945641A (en) | 2024-02-05 | 2024-02-05 | Optical fiber preform, preparation method and application thereof |
| CN202410163945.9 | 2024-02-05 |
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| WO2025168143A1true WO2025168143A1 (en) | 2025-08-14 |
| Application Number | Title | Priority Date | Filing Date |
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| PCT/CN2025/079899PendingWO2025168143A1 (en) | 2024-02-05 | 2025-02-28 | Active optical fiber preform, preparation method therefor and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117945641A (en)* | 2024-02-05 | 2024-04-30 | 中天科技精密材料有限公司 | Optical fiber preform, preparation method and application thereof |
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|---|---|---|---|---|
| CN102086089A (en)* | 2010-12-27 | 2011-06-08 | 富通集团有限公司 | Method for manufacturing rare-earth-doped fiber precast rod |
| CN102515500A (en)* | 2011-12-06 | 2012-06-27 | 长飞光纤光缆有限公司 | Preparation method for rare earth doped optical fiber preform |
| US20180282196A1 (en)* | 2017-03-30 | 2018-10-04 | Heraeus Quarzglas Gmbh & Co. Kg | Method for producing a component of rare earth metal-doped quartz glass |
| CN116854360A (en)* | 2023-07-20 | 2023-10-10 | 江苏亨通光纤科技有限公司 | Rare earth doped optical fiber preform core rod, preparation method and optical fiber |
| CN117185644A (en)* | 2023-09-01 | 2023-12-08 | 长飞光纤光缆股份有限公司 | Ytterbium-doped optical fiber preform, ytterbium-doped active optical fiber and preparation method thereof |
| CN117945641A (en)* | 2024-02-05 | 2024-04-30 | 中天科技精密材料有限公司 | Optical fiber preform, preparation method and application thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102086089A (en)* | 2010-12-27 | 2011-06-08 | 富通集团有限公司 | Method for manufacturing rare-earth-doped fiber precast rod |
| CN102515500A (en)* | 2011-12-06 | 2012-06-27 | 长飞光纤光缆有限公司 | Preparation method for rare earth doped optical fiber preform |
| US20180282196A1 (en)* | 2017-03-30 | 2018-10-04 | Heraeus Quarzglas Gmbh & Co. Kg | Method for producing a component of rare earth metal-doped quartz glass |
| CN116854360A (en)* | 2023-07-20 | 2023-10-10 | 江苏亨通光纤科技有限公司 | Rare earth doped optical fiber preform core rod, preparation method and optical fiber |
| CN117185644A (en)* | 2023-09-01 | 2023-12-08 | 长飞光纤光缆股份有限公司 | Ytterbium-doped optical fiber preform, ytterbium-doped active optical fiber and preparation method thereof |
| CN117945641A (en)* | 2024-02-05 | 2024-04-30 | 中天科技精密材料有限公司 | Optical fiber preform, preparation method and application thereof |
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