技术领域Technical field
本发明属于材料合成领域，具体涉及钡铜铅磷灰石的制备方法。The invention belongs to the field of material synthesis, and specifically relates to a preparation method of barium copper lead apatite.
背景技术Background technique
目前，一种名为铜改性铅磷灰石材料引起了极大的关注，其分子式为Pb10-xCux(PO4)6O。这种材料具有较为复杂的磁学性质，且部分研究表明该材料可能含有超导性，因此该材料具有极大的工业应用前景。Currently, a material called copper-modified lead apatite has attracted great attention, and its molecular formula is Pb10-xCux(PO4)6O. This material has relatively complex magnetic properties, and some studies have shown that the material may contain superconductivity, so this material has great industrial application prospects.
然而现有公开的技术在合成过程中，存在使用纯磷等原料，危险系数较高；制备过程中需要石英管真空封管，操作难度较大；仅含有铅铜元素，容易产生偏析导致合成失败等各种问题。面对铅铜密度和熔点不同产生铅元素聚集偏析、原料危险系数高、制备难度大等情况，本专利提出一种添加钡元素制备铜改性铅磷灰石类似物的方法，使用铅粉、磷酸二氢钠、碳酸钡、硫酸铜等较为安全的原料，在空气氛围中烧制，得到铅铜元素均匀混合的顺磁性钡铜铅磷灰石。However, the existing disclosed technology uses pure phosphorus and other raw materials during the synthesis process, which has a high risk factor; the preparation process requires vacuum sealing of quartz tubes, which is difficult to operate; it only contains lead and copper elements, which is prone to segregation and leads to synthesis failure. and other issues. Faced with the situation that the different densities and melting points of lead and copper lead to the aggregation and segregation of lead elements, the high risk factor of raw materials, and the difficulty of preparation, this patent proposes a method of adding barium element to prepare copper-modified lead apatite analogues, using lead powder, Safer raw materials such as sodium dihydrogen phosphate, barium carbonate, and copper sulfate are fired in an air atmosphere to obtain paramagnetic barium copper lead apatite with evenly mixed lead and copper elements.
顺磁性材料是一类在外磁场作用下表现出顺磁性现象的材料。顺磁性材料中的电子或原子磁矩会受到外磁场的影响，使其自旋方向与磁场方向相同或相反，从而产生磁化。顺磁性材料在实际应用中具有广泛的用途。例如，在医学影像中，顺磁性材料被用作造影剂，通过其在外磁场下的磁化特性，可以增强影像的对比度，帮助医生更准确地诊断疾病。此外，顺磁性材料还被应用于磁性存储器件、磁性传感器和磁性材料的制备等领域。Paramagnetic materials are a type of material that exhibits paramagnetic behavior under the action of an external magnetic field. The magnetic moment of electrons or atoms in paramagnetic materials will be affected by an external magnetic field, causing their spin direction to be the same or opposite to the direction of the magnetic field, thereby producing magnetization. Paramagnetic materials have a wide range of uses in practical applications. For example, in medical imaging, paramagnetic materials are used as contrast agents. Through their magnetization properties under external magnetic fields, they can enhance the contrast of images and help doctors diagnose diseases more accurately. In addition, paramagnetic materials are also used in fields such as magnetic memory devices, magnetic sensors and the preparation of magnetic materials.
发明内容Contents of the invention
本发明公开了一种顺磁性钡铜铅磷灰石的制备方法，该配方在铜改性铅磷灰石的基础上，加入钡元素掺杂，减少了铜改性铅磷灰石烧制中由于铅铜密度不同、熔点不同导致的铅铜分布集聚的问题。The invention discloses a method for preparing paramagnetic barium-copper-lead apatite. The formula is based on copper-modified lead apatite and is doped with barium element, thereby reducing the time required for firing the copper-modified lead apatite. The problem of lead and copper distribution and aggregation caused by different densities and melting points of lead and copper.
在本公开的第一方面，提供一种顺磁性钡铜铅磷灰石，所述顺磁性钡铜铅磷灰石由以下组分原料混合制成：21%～22%mol的Pb，2%～3%mol的Ba，2%～3%mol的Cu，14%～15%mol的P，59%～60%mol的O。上述组分之和为100%mol。In a first aspect of the present disclosure, a paramagnetic barium copper lead apatite is provided. The paramagnetic barium copper lead apatite is made by mixing the following raw materials: 21% to 22% mol Pb, 2% ~3% mol Ba, 2% ~ 3% mol Cu, 14% ~ 15% mol P, 59% ~ 60% mol O. The sum of the above components is 100%mol.
如上述的方面和任一可能的实现方式，上述顺磁性钡铜铅磷灰石的制备方法包括如下步骤：首先将200目铅粉、无水硫酸铜、磷酸二氢钠、碳酸钡固体粉末用混合仪震荡混合均匀，混合后加入刚玉坩埚中，然后放入到箱式电阻炉中烧制。烧制程序为经过210分钟由25℃升至1050℃，升温速率为5℃每分钟，然后在1050℃温度下保温480分钟，保温结束后停止加热，材料随炉体自然冷却。当箱式电阻炉冷却至500℃时取出，让其自然降温至室温。图1为本申请的流程图。As mentioned above and any possible implementation method, the preparation method of the above-mentioned paramagnetic barium copper lead apatite includes the following steps: first, use 200 mesh lead powder, anhydrous copper sulfate, sodium dihydrogen phosphate, and barium carbonate solid powder with Shake the mixer to mix evenly, add it to the corundum crucible after mixing, and then put it into a box-type resistance furnace for firing. The firing procedure is to increase the temperature from 25°C to 1050°C in 210 minutes, with a heating rate of 5°C per minute, and then maintain the temperature at 1050°C for 480 minutes. After the insulation is completed, the heating is stopped, and the material cools naturally with the furnace body. When the box-type resistance furnace cools to 500°C, take it out and let it cool down to room temperature naturally. Figure 1 is a flow chart of this application.
本发明的有益效果在于：The beneficial effects of the present invention are:
（1）本发明制备方法加入钡元素提高铜铅元素的互溶性，减少了铜改性铅磷灰石烧制中由于铅铜密度不同、熔点不同导致的铅铜分布集聚的问题；减少其密度差的影响，消除结晶偏析，烧结后得到顺磁性的钡铜铅磷灰石。(1) The preparation method of the present invention adds barium element to improve the mutual solubility of copper and lead elements, and reduces the problem of lead and copper distribution and aggregation caused by different densities and melting points of copper-modified lead apatite during the firing of copper-modified lead apatite; reducing its density The influence of the difference is eliminated, crystallization segregation is eliminated, and paramagnetic barium copper lead apatite is obtained after sintering.
（2）本发明在烧制过程中不需要严格的真空条件和烧制气氛要求，解决了现有技术中危险系数较高、需要石英管真空封管、操作难度较大的技术难题。(2) The present invention does not require strict vacuum conditions and firing atmosphere requirements during the firing process, and solves the technical problems in the existing technology that have a high risk factor, require vacuum sealing of quartz tubes, and are difficult to operate.
（3）现有的合成过程中，存在使用纯磷等原料合成磷化亚铜前驱体，合成过程危险系数较高的问题。为了解决上述问题，本申请提出一种使用铅粉、磷酸二氢钠、碳酸钡、硫酸铜等较为安全的原料制备顺磁性钡铜铅磷灰石的方法，解决了现有技术难题。(3) In the existing synthesis process, there is a problem that the cuprous phosphide precursor is synthesized using raw materials such as pure phosphorus, and the synthesis process has a high risk factor. In order to solve the above problem, this application proposes a method for preparing paramagnetic barium copper lead apatite using relatively safe raw materials such as lead powder, sodium dihydrogen phosphate, barium carbonate, and copper sulfate, which solves the existing technical problems.
（4）本发明合成的钡铜铅磷灰石为顺磁性，呈现出典型的顺磁现象。(4) The barium copper lead apatite synthesized by the present invention is paramagnetic and exhibits a typical paramagnetic phenomenon.
（5）该合成方法相较于传统的合成法具有合成方法简单、合成时间短，合成步骤少等优点。(5) Compared with traditional synthesis methods, this synthesis method has the advantages of simple synthesis method, short synthesis time, and fewer synthesis steps.
附图说明Description of drawings
图1为本发明流程图；Figure 1 is a flow chart of the present invention;
图2为实施例1的XRD图谱；Figure 2 is the XRD pattern of Example 1;
图3为实施例1的变温磁滞回线（M-T曲线）；Figure 3 is the variable temperature hysteresis loop (M-T curve) of Example 1;
图4为实施例1在10K，300K下的磁化曲线；Figure 4 is the magnetization curve of Example 1 at 10K and 300K;
图5为实施例1的SEM和EDS图像；Figure 5 is the SEM and EDS images of Example 1;
图6为实施例2的XRD图谱；Figure 6 is the XRD pattern of Example 2;
图7为实施例2的变温磁滞回线（M-T曲线）；Figure 7 is the variable temperature hysteresis loop (M-T curve) of Example 2;
图8为实施例2在10K，300K下的磁化曲线；Figure 8 is the magnetization curve of Example 2 at 10K and 300K;
图9为实施例2的SEM和EDS图像。Figure 9 is the SEM and EDS images of Example 2.
具体实施方式Detailed ways
实施例一：Example 1:
将10.4641g的铅粉（200目）、0.8355g的无水硫酸铜、4.0926g的磷酸二氢钠、1.6086g的碳酸钡固体粉末用混合仪震荡混合均匀，混合后放入刚玉坩埚中。Mix 10.4641g of lead powder (200 mesh), 0.8355g of anhydrous copper sulfate, 4.0926g of sodium dihydrogen phosphate, and 1.6086g of barium carbonate solid powder with a mixer and mix evenly, then put them into a corundum crucible.
将混合后的样品放入箱式电阻炉中烧制，烧制程序为210分钟由25℃升至1050℃，升温速率5℃/min。升温到1050℃后保温反应480分钟，反应结束后自然冷却。The mixed sample was put into a box-type resistance furnace and fired. The firing procedure was from 25°C to 1050°C in 210 minutes, with a heating rate of 5°C/min. After the temperature was raised to 1050°C, the reaction was maintained for 480 minutes, and then cooled naturally after the reaction was completed.
当箱式电阻炉冷却至500℃时取出材料，让其自然降温至室温。When the box-type resistance furnace cools to 500°C, take out the material and let it cool down to room temperature naturally.
图2为本实施例的XRD粉末衍射结果，可以看出产物中含有钡铜铅磷灰石；图3为本实施例的变温磁滞回线（M-T曲线），图4为本实施例在10K，300K下的磁化曲线，呈现出典型的顺磁现象，证明本实施例合成的钡铜铅磷灰石为顺磁性；图5为本实施例的SEM和EDS图像，EDS图像表明铅铜钡元素在空间上分布均匀，而不是互补的，证明加入钡元素能够促进铅铜元素均匀混合；Figure 2 is the XRD powder diffraction result of this embodiment, and it can be seen that the product contains barium copper lead apatite; Figure 3 is the variable temperature hysteresis loop (M-T curve) of this embodiment, and Figure 4 is the temperature of this embodiment at 10K , the magnetization curve at 300K shows a typical paramagnetic phenomenon, proving that the barium copper lead apatite synthesized in this embodiment is paramagnetic; Figure 5 shows the SEM and EDS images of this embodiment. The EDS image shows that the lead, copper, and barium elements are in space. The distribution on the surface is uniform, rather than complementary, proving that adding barium element can promote the uniform mixing of lead and copper elements;
实施例二：Example 2:
将5.2114g的铅粉（200目）、0.4239g的无水硫酸铜、2.0223g的磷酸二氢钠、0.7106g的碳酸钡固体粉末用混合仪震荡混合均匀，混合后放入刚玉坩埚中。Mix 5.2114g of lead powder (200 mesh), 0.4239g of anhydrous copper sulfate, 2.0223g of sodium dihydrogen phosphate, and 0.7106g of barium carbonate solid powder with a mixer and mix evenly, then put them into a corundum crucible after mixing.
将混合后的样品放入箱式电阻炉中烧制，烧制程序为210分钟由25℃升至1050℃，升温速率5℃/min。升温到1050℃后保温反应480分钟，反应结束后自然冷却。The mixed sample was put into a box-type resistance furnace and fired. The firing procedure was from 25°C to 1050°C in 210 minutes, with a heating rate of 5°C/min. After the temperature was raised to 1050°C, the reaction was maintained for 480 minutes, and then cooled naturally after the reaction was completed.
当箱式电阻炉冷却至500℃时取出材料，让其自然降温至室温。When the box-type resistance furnace cools to 500°C, take out the material and let it cool down to room temperature naturally.
图6为本实施例的XRD粉末衍射结果，可以看出产物中含有钡铜铅磷灰石；图7为本实施例的变温磁滞回线（M-T曲线），图8为本实施例在10K，300K下的磁化曲线，呈现出典型的顺磁现象，证明本实施例合成的钡铜铅磷灰石为顺磁性；图9为本实施例的SEM和EDS图像，EDS图像表明铅铜钡元素在空间上分布均匀，而不是互补的，证明加入钡元素能够促进铅铜元素均匀混合；Figure 6 is the XRD powder diffraction result of this embodiment, and it can be seen that the product contains barium copper lead apatite; Figure 7 is the variable temperature hysteresis loop (M-T curve) of this embodiment, and Figure 8 is this embodiment at 10K , the magnetization curve at 300K shows a typical paramagnetic phenomenon, proving that the barium copper lead apatite synthesized in this embodiment is paramagnetic; Figure 9 shows the SEM and EDS images of this embodiment. The EDS image shows that the lead, copper, and barium elements are in space. The distribution on the surface is uniform, rather than complementary, proving that adding barium element can promote the uniform mixing of lead and copper elements;
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围、发明原理所做的等效变化，皆应属本发明的涵盖范围。The above are only preferred embodiments of the present invention, and any equivalent changes made based on the patentable scope and inventive principles of the present invention shall fall within the scope of the present invention.
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| CN202311801752.3ACN117756082A (en) | 2023-12-26 | 2023-12-26 | Preparation method of paramagnetic barium copper lead apatite |
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| CN202311801752.3ACN117756082A (en) | 2023-12-26 | 2023-12-26 | Preparation method of paramagnetic barium copper lead apatite |
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