技术领域technical field
本发明涉及材料微结构的获得与分析技术领域，具体是一种利用液滴冷却实现高速降温的装置及方法。The invention relates to the technical field of obtaining and analyzing material microstructures, in particular to a device and method for realizing high-speed cooling by using droplet cooling.
背景技术Background technique
工业上常以高于1000K/s的降温速率将样品从熔体淬冷为固体(例如注塑、吹膜等)，在这样一个复杂的过程中可以形成具有不同程度有序结构以及重组结构的材料，包括一些高分子、金属、共混物以及合金等。而最近快速发展的添加剂技术以及3D打印技术中也涉及到少量熔体快速冷却的过程，因此以实验方法模拟工业快速冷却，了解微量材料(从纳克到几十微克)的淬冷过程是非常重要的，这可以帮助我们了解在工业上涉及的快速冷却过程中材料内具体发生了什么，从而可以更好的指导未来的工业生产。In the industry, the sample is often quenched from the melt to a solid at a cooling rate higher than 1000K/s (such as injection molding, blown film, etc.), and materials with different degrees of ordered structure and restructured structure can be formed in such a complex process , including some polymers, metals, blends and alloys. The recent rapid development of additive technology and 3D printing technology also involves the process of rapid cooling of a small amount of melt. Therefore, it is very important to simulate industrial rapid cooling by experimental methods to understand the quenching process of trace materials (from nanograms to tens of micrograms). Importantly, this can help us understand what exactly happens inside the material during the rapid cooling process involved in industry, which can better guide future industrial production.
金属和高分子都是非常重要的材料，都需要传统手段无法达到的降温速率。通过减少样品尺寸，使用气体冷却，可以实现可控的高速降温。超快扫描量热仪 (FSC)便是这样一种在高速升降温过程中观测材料的杰出技术手段。它不仅可以制备具有精确热历史的样品，同时可以在很高的扫描速率下对其进行分析，通过超高速扫描(通常是100000K/s以上)，捕获微小样品在不同温度或时间时的结构快照。但是FSC的快速扫描也具有其局限性，特别是对样品质量的要求以及当样品温度达到周围环境温度时对扫描速率的影响。Both metals and polymers are very important materials, and both require cooling rates that cannot be achieved by traditional means. By reducing the sample size and using gas cooling, controlled high-speed cooling can be achieved. Ultrafast Scanning Calorimetry (FSC) is one such outstanding technique for observing materials during rapid heating and cooling. It can not only prepare samples with precise thermal history, but also analyze them at a very high scanning rate. Through ultra-high-speed scanning (usually above 100,000K/s), it can capture the structural snapshots of tiny samples at different temperatures or times. . But the fast scanning of FSC also has its limitations, especially the requirements on the sample quality and the influence on the scanning rate when the sample temperature reaches the ambient temperature.
由于气体具有极佳的导热系数和热容，热惯性较低，当样品需要快速从加热切换到冷却时，使用空气冷却是非常有效的。但是，同样也是因为这些气体性质，当样品与气体之间的温差趋近于零时，降温效率会非常明显的受到限制。实际上， FSC使用的传感器只有在温度高于气体温度500K时才能够实现106K/s的降温速率，当温度高于炉温100K时只能达到1000K/s，而高于炉温50K时则只能达到100K/s。当温度达到特定值以下后降温速率急剧下降，这种现象被称作弹道冷却(如图1所示)，尤其对于质量较大的样品，弹道冷却的影响尤其明显。如果以氦气代替空气则可以明显减少弹道冷却，或者可以通过降低气体温度从而在特定的温度避免弹道冷却，比如说在液氮冷却的空气或氦气中进行实验。但这种方法也不是总是可行的，会受到实验平台和测试条件的影响。Due to the excellent thermal conductivity and heat capacity of gases and the low thermal inertia, the use of air cooling is very efficient when samples need to be switched from heating to cooling quickly. However, also because of these gas properties, when the temperature difference between the sample and the gas approaches zero, the cooling efficiency will be significantly limited. In fact, the sensor used by FSC can only achieve a cooling rate of 106 K/s when the temperature is 500K higher than the gas temperature. When the temperature is 100K higher than the furnace temperature, it can only reach 1000K/s. It can only reach 100K/s. When the temperature drops below a certain value, the cooling rate drops sharply. This phenomenon is called ballistic cooling (as shown in Figure 1), especially for samples with a larger mass, the impact of ballistic cooling is particularly obvious. Ballistic cooling can be significantly reduced if helium is used instead of air, or ballistic cooling can be avoided at certain temperatures by lowering the gas temperature, such as experiments in liquid nitrogen cooled air or helium. However, this method is not always feasible and will be affected by the experimental platform and test conditions.
发明内容Contents of the invention
发明目的：针对现有技术中的上述缺陷，本申请提供了一种以液体降温代替气体降温、达到更高降温速率的高速降温装置，并提供了利用该装置实现高速降温的方法。Purpose of the invention: In view of the above defects in the prior art, this application provides a high-speed cooling device that uses liquid cooling instead of gas cooling to achieve a higher cooling rate, and provides a method for using the device to achieve high-speed cooling.
技术方案：本发明所述的一种利用液滴冷却实现微量材料高速降温的装置，包括：注射器，与注射驱动器相连接，用于滴加挥发性冷却液体；置于注射器正下方的温度传感器，包括热电堆冷端和热端，内置有加热电阻器，表面附有氮化硅薄膜，微量材料即置于氮化硅薄膜上；数据采集器，用于采集温度传感器的热电堆信号和加热电阻器信号；气体吹扫设备；控制中心，所述注射器、温度传感器、数据采集器以及气体吹扫设备均与控制中心相连接。Technical solution: A device for realizing high-speed cooling of trace materials by using droplet cooling according to the present invention, comprising: a syringe connected to an injection driver for dripping volatile cooling liquid; a temperature sensor placed directly below the syringe, Including thermopile cold end and hot end, built-in heating resistor, silicon nitride film attached on the surface, trace material is placed on the silicon nitride film; data collector, used to collect thermopile signal and heating resistance of temperature sensor signal; gas purging equipment; control center, the injector, temperature sensor, data collector and gas purging equipment are all connected to the control center.
其中，所述装置需要通过注射驱动器和注射器控制冷却液滴的大小和流速，确保冷却液滴首先接触样品的表面而不是传感器的薄膜，在这种情况下冷却效率最高。Among them, the device needs to control the size and flow rate of the cooling liquid droplet through the injection driver and the injector, so as to ensure that the cooling liquid droplet contacts the surface of the sample first rather than the film of the sensor, in which case the cooling efficiency is the highest.
用于注射液滴的注射器可以是任何一种可以使液体形成稳定细流或者液滴的装置，例如医用注射器和普通PE滴管均可以。也可以是其他注射装置，比如微流控装置等。需要注意的是，液滴的直径需要大于样品的直径，液滴的直径越大，冷却的效率越高。一般情况下，直径大约2mm的液滴即可实现高速降温。The syringe used for injecting liquid droplets can be any device that can form a steady stream or droplets of liquid, such as medical syringes and common PE droppers. It can also be other injection devices, such as microfluidic devices and the like. It should be noted that the diameter of the droplet needs to be larger than the diameter of the sample, and the larger the diameter of the droplet, the higher the cooling efficiency. In general, droplets with a diameter of about 2mm can achieve high-speed cooling.
进一步的，所述冷却液体为具有一定挥发性的液体，在样品冷却之后可通过干燥的气流吹扫，在环境温度下去除冷却用液滴且不改变样品的热历史。由于莱顿弗洛斯特效应，液体挥发太快会导致其在热的传感器上沸腾，从而影响降温的效率，甚至中断冷却；另外当传感器测试面积不同时冷却液滴的沸腾情况也不同，因此需要根据不同面积的传感器选择不同性质的冷却液体。Further, the cooling liquid is a liquid with certain volatility, and after the sample is cooled, it can be purged by a dry air flow to remove the cooling liquid droplets at ambient temperature without changing the thermal history of the sample. Due to the Leiden Frost effect, too fast liquid volatilization will cause it to boil on the hot sensor, thereby affecting the cooling efficiency, or even interrupting the cooling; in addition, when the sensor test area is different, the boiling conditions of the cooling droplet are also different, so it is necessary to Different properties of cooling liquids are selected according to sensors of different areas.
优选的，所述冷却液体为冷乙醇，温度范围是-50℃到0℃。优选-20℃。Preferably, the cooling liquid is cold ethanol, and the temperature range is -50°C to 0°C. Preferably -20°C.
任何不溶解或者不吸收冷却液体的样品均可以使用于该装置，根据所使用温度传感器的加热面积，样品的直径可从几微米到几百微米不等。Any sample that does not dissolve or absorb the cooling liquid can be used in the device, and the diameter of the sample can vary from a few microns to hundreds of microns, depending on the heated area of the temperature sensor used.
所述温度传感器为任何目前可用的商用真空规薄膜传感器(XENSOR.NL)，例如XI394，XI395和XI400等。进一步的，本申请中采用的所述XI394测量区域为8×6μm2、XI395测量区域为60×60μm2、XI400测量区域直径为500μm。The temperature sensor is any currently available commercial vacuum gauge film sensor (XENSOR.NL), such as XI394, XI395 and XI400, etc. Further, the XI394 measurement area used in this application is 8×6 μm2 , the XI395 measurement area is 60×60 μm2 , and the XI400 measurement area is 500 μm in diameter.
传感器上的加热电阻器，可根据需要在降温前将样品预热到某个指定温度，由于加热所需电压以及传感器上加热电阻材质的限制，样品在金制传感器上的加热范围为0-1300K，在铝制传感器的加热范围为0-800K。The heating resistor on the sensor can preheat the sample to a specified temperature before cooling down as needed. Due to the voltage required for heating and the limitation of the heating resistor material on the sensor, the heating range of the sample on the gold sensor is 0-1300K , the heating range of the aluminum sensor is 0-800K.
所述气体吹扫设备的吹扫气流可以是干燥的氮气，也可以是空气、氩气等，具体根据使用环境以及测试样品而定，以便于在不改变样品温度的情况下去除冷却液滴。The purge gas flow of the gas purge device can be dry nitrogen, air, argon, etc., depending on the use environment and the test sample, so as to remove the cooling liquid droplets without changing the temperature of the sample.
使用该装置的整个降温过程，冷却速率在106K/s以上，因此可以在10ms以内完成液滴接近到完成冷却的整个降温过程。In the entire cooling process using the device, the cooling rate is above 106 K/s, so the entire cooling process from the approach of the liquid droplet to the completion of cooling can be completed within 10 ms.
一种改进型快速扫描量热仪，集成有上述利用液滴冷却实现微量材料高速降温的装置。An improved rapid scanning calorimeter is integrated with the above-mentioned device for realizing high-speed cooling of trace materials by means of liquid droplet cooling.
进一步的，所述利用液滴冷却实现微量材料高速降温的装置附着于快速扫描量热仪的样品室内，包括但不仅限于室温敞开平台，冷热台，真空管等，并有效实现降温速率的进一步提高，且不影响进一步的快速热分析和结构分析。Further, the device for achieving high-speed cooling of trace materials by using droplet cooling is attached to the sample chamber of the rapid scanning calorimeter, including but not limited to open platforms at room temperature, hot and cold tables, vacuum tubes, etc., and effectively achieves a further increase in cooling rate , without affecting further rapid thermal analysis and structural analysis.
其中，所述快速扫描量热仪可以为目前可用的FSC设备，例如针对敞开室温体系、冷热台型密闭体系以及Tube-dewar型都可以进行配件叠加。Wherein, the fast scanning calorimeter can be the currently available FSC equipment, for example, accessories can be stacked for the open room temperature system, the cold and hot table type closed system and the Tube-dewar type.
一种利用上述装置实现微量材料高速降温的方法，包括以下步骤：A method for realizing high-speed cooling of trace materials by using the above-mentioned device, comprising the following steps:
(1)样品预热：取样品放置在温度传感器的氮化硅薄膜上，利用温度传感器上的加热电阻器将样品预热到指定温度；(1) Sample preheating: take the sample and place it on the silicon nitride film of the temperature sensor, and use the heating resistor on the temperature sensor to preheat the sample to the specified temperature;
(2)高速降温和数据采集：通过注射器将冷却液体以液滴的形式滴加或喷射到经过步骤(1)预热后的样品表面，由数据采集器跟踪液滴接近过程中热电堆信号的变化，当液滴接近样品时，样品的温度开始降低，用于跟踪样品温度的热电堆信号偏离步骤(1)设定的指定温度，当样品降低的温差ΔT大于预先设定的触发值ΔTtrigger时，触发关闭加热电阻器；同时，对样品温度以微秒级的精度不间断的进行监控，监测降温的速率以及样品可能发生的相转变，并采集数据，进行后续数据分析；(2) High-speed cooling and data acquisition: the cooling liquid is dripped or sprayed in the form of droplets to the surface of the sample preheated in step (1) through the syringe, and the data collector tracks the temperature of the thermopile signal during the approach of the droplets. Change, when the droplet approaches the sample, the temperature of the sample begins to drop, and the thermopile signal used to track the sample temperature deviates from the specified temperature set in step (1), when the temperature difference ΔT of the sample drop is greater than the preset trigger value ΔTtrigger At the same time, the temperature of the sample is continuously monitored with microsecond precision, the cooling rate and the possible phase transition of the sample are monitored, and the data is collected for subsequent data analysis;
(3)样品干燥：根据步骤(2)的采集数据显示完成冷却后，通过控制中心启动气体吹扫设备去除冷却液滴，无液滴残留的样品可以原位进行样品材料的快速热分析或结构分析，完成高速降温。(3) Sample drying: According to the collected data in step (2), after the cooling is completed, the gas purging equipment is activated through the control center to remove the cooling liquid droplets, and the samples without liquid droplets remaining can be used for rapid thermal analysis or structural analysis of the sample material in situ Analysis, complete high-speed cooling.
步骤(1)中的指定温度需要具体根据实验要求设置，样品的指定温度一般最大范围可为100K-800K。当使用金制传感器则样品的最大温度范围可以为 100K-1300K。The specified temperature in step (1) needs to be set according to the experimental requirements, and the maximum range of the specified temperature of the sample can generally be 100K-800K. When using a gold sensor the maximum temperature range of the sample can be 100K-1300K.
步骤(2)中，由数据采集器控制的内触发过程可在微秒内实现，能够在液滴触碰到样品之前跟踪液滴的接近过程，并且在需要时关闭针对样品的温度控制系统(即加热电阻器)以达到最佳的冷却速率，加热电阻器关的过早或过晚都会影响降温速率。在降温过程中对样品的温度以微秒级的精度不间断的进行监控，温度信号可以显示降温的速率以及样品可能的相转变。In step (2), the internal trigger process controlled by the data collector can be realized within microseconds, which can track the approaching process of the droplet before it touches the sample, and shut down the temperature control system for the sample when needed ( That is, the heating resistor) to achieve the best cooling rate, the heating resistor is turned off too early or too late will affect the cooling rate. During the cooling process, the temperature of the sample is continuously monitored with microsecond accuracy, and the temperature signal can display the cooling rate and the possible phase transition of the sample.
由于冷端的参考温度采用的是环境温度，当热电堆信号的参考温度(冷端) 不可靠时，比如说当液滴温度比传感器的温度低很多时，可以使用传感器上已有的加热电阻器进行温度测量和校正。Since the reference temperature of the cold junction is the ambient temperature, when the reference temperature (cold junction) of the thermopile signal is not reliable, for example, when the temperature of the droplet is much lower than the temperature of the sensor, the existing heating resistor on the sensor can be used Perform temperature measurements and corrections.
由于冷却液滴的温度低于预热后的样品温度，再加上液滴的接触以及加热器的关闭，可以实现对样品的快速降温。Since the temperature of the cooling liquid droplet is lower than the temperature of the sample after preheating, coupled with the contact of the liquid droplet and the shutdown of the heater, the rapid cooling of the sample can be realized.
步骤(1)中，任何不溶解或者不吸收冷却液体的样品均可以使用于该装置，根据所使用温度传感器的加热面积，样品的直径可从几微米到几百微米不等。In step (1), any sample that does not dissolve or absorb the cooling liquid can be used in the device, and the diameter of the sample can vary from a few microns to hundreds of microns depending on the heating area of the temperature sensor used.
步骤(2)中，所述冷却液体为冷乙醇，温度范围是-50℃到0℃，优选-20℃。In step (2), the cooling liquid is cold ethanol, and the temperature range is from -50°C to 0°C, preferably -20°C.
步骤(3)中，样品冷却之后需要通过干燥的气流吹扫，在环境温度下去除冷却用液滴，不改变样品的热历史。所述气体吹扫气体流量为0-10L/min，吹扫时间可自由设定。对于乙醇可选择1L/min吹扫30s。在快速冷却之后，可以原位对样品进行快速热分析，包括再升温分析降温后样品的结构，或者做进一步的热处理，比如说等温或者非等温实验；也可以进行其它的形貌表征或力学表征，不需要转移到其它设备上。In step (3), after the sample is cooled, it needs to be purged by a dry air flow to remove the cooling droplets at ambient temperature without changing the thermal history of the sample. The flow rate of the gas purging gas is 0-10L/min, and the purging time can be set freely. For ethanol, you can choose to purge at 1L/min for 30s. After rapid cooling, rapid thermal analysis can be performed on the sample in situ, including reheating to analyze the structure of the sample after cooling, or further heat treatment, such as isothermal or non-isothermal experiments; other morphological or mechanical characterizations can also be performed , does not need to be transferred to other devices.
有益效果：本申请所述的高速降温装置通过冷媒液滴接触样品以及程序控制快速响应关闭加热器，可达到高于一般气体冷却的降温速率；同时通过采集热电堆信号或加热电阻器信号可跟踪降温的速率以及样品可能发生的相转变；使用挥发性液体，通过气体吹扫去除冷却液滴后可原位进行下一步热处理或者形貌表征。本申请所述的高速降温方法可用于获取样品材料的特殊物相，可与现有的超快扫描量热技术结合，拓展对微量样品高速降温的速率，实现模拟工业淬冷过程，同时对高速降温获得的材料进行原位热分析及微结构表征。Beneficial effects: the high-speed cooling device described in this application can achieve a cooling rate higher than that of general gas cooling by contacting the sample with the refrigerant droplet and quickly responding to the program control to turn off the heater; at the same time, it can be tracked by collecting thermopile signals or heating resistor signals The rate of cooling and the possible phase transition of the sample; using a volatile liquid, the next step of heat treatment or morphology characterization can be performed in situ after removing the cooling droplets by gas purging. The high-speed cooling method described in this application can be used to obtain the special phase of the sample material, and can be combined with the existing ultra-fast scanning calorimetry technology to expand the rate of high-speed cooling for trace samples and realize the simulation of the industrial quenching process. The obtained materials were subjected to in-situ thermal analysis and microstructural characterization.
比如对于一些结晶非常快的工业级树脂(例如均相成核的聚乙烯PE或者聚四氟乙烯PTFE)，即使是使用气体冷却极小质量的样品也无法满足其降温速率的要求，而金属材料的结晶速度则更快。在这种情况下，额外的液体冷却就会有很大帮助。这种利用液滴冷却实现高速降温的方法可以结合已有的快速扫描量热仪，根据降温速率要求、使用环境以及仪器联用情况的不同，实现高速降温并进行后续的量热表征及其它显微结构表征，获得这些互补的信息可以帮助更全面的解释快速冷却的影响以及快速冷却后制得的塑料或金属合金产品的性能。使用液体进行额外的冷却可以大大扩展传统FSC的局限性，同时也使其成为一种非常具有工业吸引力的仪器。For example, for some industrial-grade resins with very fast crystallization (such as polyethylene PE or polytetrafluoroethylene PTFE with homogeneous nucleation), even the use of gas to cool samples with a very small mass cannot meet the cooling rate requirements, and metal materials The crystallization rate is faster. In this case, additional liquid cooling can help a lot. This method of using droplet cooling to achieve high-speed cooling can be combined with the existing fast scanning calorimeter to achieve high-speed cooling and carry out subsequent calorimetric characterization and other displays according to the cooling rate requirements, operating environment and instrument connection conditions. Microstructural characterization, obtaining this complementary information can help to more fully explain the effects of rapid cooling and the properties of plastic or metal alloy products produced after rapid cooling. The use of liquids for additional cooling can greatly expand the limitations of conventional FSCs, while also making it a very industrially attractive instrument.
附图说明Description of drawings
图1是弹道冷却示意图；Fig. 1 is a schematic diagram of ballistic cooling;
图2是利用液滴冷却实现微量材料高速降温的装置基本结构示意图；Figure 2 is a schematic diagram of the basic structure of a device that uses droplet cooling to achieve high-speed cooling of trace materials;
图3是本申请装置结构示意图；Fig. 3 is the schematic diagram of the device structure of the present application;
图4是冷却过程详细示意图；Fig. 4 is a detailed schematic diagram of the cooling process;
图5是液体冷却工作原理示意图；Figure 5 is a schematic diagram of the working principle of liquid cooling;
图6是本申请步骤2触发关闭加热电阻器过程示意图；Fig. 6 is a schematic diagram of the process of triggering and closing the heating resistor in step 2 of the present application;
图7为液体冷却装置与已有的快速扫描量热仪FSC组合的简要原理示意图；Fig. 7 is a brief schematic diagram of the combination of a liquid cooling device and an existing fast scanning calorimeter FSC;
图8 tube-dewar型气体冷却FSC装置以及液体冷却装置与tube-dewar型FSC 装置的组合的对比示意图；Figure 8. Schematic diagram of the comparison of the tube-dewar type gas-cooled FSC device and the combination of the liquid cooling device and the tube-dewar type FSC device;
图9为本申请液体冷却效果与传统的气体冷却效果的对比图；Fig. 9 is a comparison diagram between the liquid cooling effect of the present application and the traditional gas cooling effect;
图10为使用冷乙醇作为冷却液体，在不同面积大小的传感器上使用的冷却效果对比图，传感器面积越小，液体的沸腾越少，可以达到的降温速率越高。Figure 10 is a comparison diagram of the cooling effect of sensors with different area sizes using cold ethanol as the cooling liquid. The smaller the sensor area, the less the liquid boils, and the higher the cooling rate that can be achieved.
具体实施方式Detailed ways
下面结合具体实施例对本申请作出详细说明。The present application will be described in detail below in conjunction with specific embodiments.
实施例1Example 1
如图2和图3所示的利用液滴冷却实现微量材料高速降温的装置，包括：注射器，其与注射驱动器相连接，用于滴加挥发性冷却液体；置于注射器正下方的温度传感器，包括热电堆冷端和热端，内置有加热电阻器，表面附有氮化硅薄膜，微量材料即置于氮化硅薄膜上；数据采集器，用于采集温度传感器的热电堆信号和加热电阻器信号；气体吹扫设备，用于完成冷却后的样品吹扫；控制中心，所述注射器、温度传感器、数据采集器以及气体吹扫设备均与控制中心电连接。As shown in Figure 2 and Figure 3, the device for realizing high-speed cooling of trace materials by using droplet cooling includes: a syringe connected to an injection driver for dripping volatile cooling liquid; a temperature sensor placed directly below the syringe, Including thermopile cold end and hot end, built-in heating resistor, silicon nitride film attached on the surface, trace material is placed on the silicon nitride film; data collector, used to collect thermopile signal and heating resistance of temperature sensor The signal of the device; the gas purging equipment is used to complete the purging of the cooled sample; the control center, the injector, the temperature sensor, the data collector and the gas purging equipment are all electrically connected to the control center.
实施例2Example 2
利用实施例1所述装置实现微量材料高速降温的方法，如图4所示，包括以下步骤：The method of utilizing the device described in Example 1 to realize high-speed cooling of trace materials, as shown in Figure 4, comprises the following steps:
(1)样品预热：取样品放置在温度传感器的氮化硅薄膜上，利用温度传感器上的加热电阻器将样品预热到指定温度；(1) Sample preheating: take the sample and place it on the silicon nitride film of the temperature sensor, and use the heating resistor on the temperature sensor to preheat the sample to the specified temperature;
(2)高速降温和数据采集：通过注射器将冷却液体以液滴的形式滴加或喷射到经过步骤(1)预热后的样品表面，由数据采集器跟踪液滴接近过程中热电堆信号的变化，如图5和图6所示，当液滴接近样品时，样品的温度开始降低，用于跟踪样品温度的热电堆信号偏离步骤(1)设定的指定温度，当样品降低的温差ΔT大于预先设定的触发值ΔTtrigger时，触发关闭加热电阻器；同时，对样品温度以微秒级的精度不间断的进行监控，监测降温的速率以及样品可能发生的相转变，并采集数据，进行后续数据分析；(2) High-speed cooling and data acquisition: the cooling liquid is dripped or sprayed in the form of droplets to the surface of the sample preheated in step (1) through the syringe, and the data collector tracks the temperature of the thermopile signal during the approach of the droplets. Changes, as shown in Figure 5 and Figure 6, when the droplet approaches the sample, the temperature of the sample begins to decrease, and the thermopile signal used to track the sample temperature deviates from the specified temperature set in step (1), when the temperature difference ΔT of the sample decreases When it is greater than the preset trigger value ΔTtrigger , the heating resistor is triggered to be turned off; at the same time, the temperature of the sample is continuously monitored with microsecond accuracy, the cooling rate and the possible phase transition of the sample are monitored, and data is collected. carry out subsequent data analysis;
(3)样品干燥：根据步骤(2)的采集数据显示完成冷却后，在环境温度下，通过控制中心启动气体吹扫设备去除冷却液滴，无液滴残留的样品可以原位进行样品材料的快速热分析或结构分析，完成高速降温。(3) Sample drying: According to the collected data in step (2), after the cooling is completed, at ambient temperature, start the gas purging equipment through the control center to remove the cooling liquid droplets, and the samples without residual liquid droplets can be dried in situ. Rapid thermal analysis or structural analysis to complete high-speed cooling.
其中，步骤(2)中，冷却液体为温度范围是-20℃的冷乙醇；步骤(1)中，指定温度范围是100K-800K，当使用金制传感器则样品的最大温度范围可以为 100K-1300K。；步骤(3)中，所述气体吹扫设备吹扫气体流量为1L/min吹扫30s。Among them, in step (2), the cooling liquid is cold ethanol with a temperature range of -20°C; in step (1), the specified temperature range is 100K-800K, and when a gold sensor is used, the maximum temperature range of the sample can be 100K- 1300K. ; In step (3), the purge gas flow rate of the gas purging equipment is 1L/min for 30s.
对比例1Comparative example 1
采用实施例1所示的装置和现有传统的气体冷却装置在同等条件下进行冷却操作，结果如图9所示，由图可见，液滴冷却(黑色实线)明显优于气氛冷却(灰色虚线)的降温速率性能。线性坐标-a，双对数坐标-b。Adopt the device shown in embodiment 1 and existing traditional gas cooling device to carry out cooling operation under the same conditions, the result is as shown in Figure 9, as can be seen from the figure, droplet cooling (black solid line) is obviously better than atmosphere cooling (gray Dotted line) cooling rate performance. Linear coordinates-a, log-logarithmic coordinates-b.
对比例2Comparative example 2
我们利用实施例1所示装置在几种不同规格的传感器上进行了液滴冷却和气体冷却性能的对比实验，所述传感器包括XI394(测量区域8x6μm2)、XI395 (测量区域60x60μm2)以及XI400(测量区域直径500μm)，试验结果如图10 所示，对比数据如下表所示，由此可见，XI400传感器(UHC-1Flash DSC传感器，直径500μm，2μm厚)上冷乙醇的沸腾降低了液体冷却的性能(灰色曲线)，但是仍然比原来的慢速降温(黑色曲线)好很多。灰色曲线是相同温度时在XI395 传感器(60x80μm2,1μm厚)上进行液体冷却(灰色虚线)或者传统降温(黑色虚线)的结果。由此可见，传感器面积对降温效果有较大影响，传感器面积越大，冷却液体的沸腾现象越严重，降温速率越低。但是即使是测试面积最大的 XI400传感器，使用额外的液滴冷却所能达到的降温速率也比传统的气体冷却效果要好很多。We used the device shown in Example 1 to conduct comparative experiments on the performance of droplet cooling and gas cooling on several sensors with different specifications, including XI394 (measurement area 8x6μm2 ), XI395 (measurement area 60x60μm2 ) and XI400 (The diameter of the measurement area is 500 μm), the test results are shown in Figure 10, and the comparative data are shown in the table below, it can be seen that the boiling of cold ethanol on the XI400 sensor (UHC-1Flash DSC sensor, 500 μm in diameter, 2 μm thick) reduces the liquid cooling performance (grey curve), but still much better than the original slow cooling (black curve). The gray curve is the result of liquid cooling (dashed gray line) or conventional cooling (dashed black line) on an XI395 sensor (60x80 μm2 , 1 μm thick) at the same temperature. It can be seen that the sensor area has a great influence on the cooling effect, and the larger the sensor area, the more serious the boiling phenomenon of the cooling liquid and the lower the cooling rate. But even for the XI400 sensor with the largest tested area, the cooling rate achievable with additional droplet cooling is much better than conventional gas cooling.
实施例3Example 3
如图8所示，一种集成有实施例1所述装置的Tube-dewar型快速扫描量热仪 FSC，将实施例1的装置的样品舱放入杜瓦罐中的真空管，其基本原理图如图7 所示，由于装有传感器的炉子可以保持非常低的温度(大概80K)，其可用的温度范围以及扫描速率可以大大提高，再加上额外的液滴冷却装置，可以达到目前快速扫描量热仪最快的降温速率。As shown in Figure 8, a kind of Tube-dewar type fast scanning calorimeter FSC that is integrated with the device described in embodiment 1, puts the sample compartment of the device of embodiment 1 into the vacuum tube in the Dewar tank, its basic principle diagram As shown in Figure 7, since the furnace equipped with sensors can maintain a very low temperature (about 80K), its usable temperature range and scanning rate can be greatly improved, and with the addition of an additional droplet cooling device, the current fast scanning can be achieved. The fastest cooling rate of the calorimeter.
| Application Number | Priority Date | Filing Date | Title |
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| CN201711077303.3ACN107884259B (en) | 2017-11-06 | 2017-11-06 | Device and method for realizing high-speed cooling of trace materials by using droplet cooling |
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| CN201711077303.3ACN107884259B (en) | 2017-11-06 | 2017-11-06 | Device and method for realizing high-speed cooling of trace materials by using droplet cooling |
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| CN201711077303.3AActiveCN107884259B (en) | 2017-11-06 | 2017-11-06 | Device and method for realizing high-speed cooling of trace materials by using droplet cooling |
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