CN107884259B - Device and method for realizing high-speed cooling of trace materials by utilizing liquid drop cooling - Google Patents
Device and method for realizing high-speed cooling of trace materials by utilizing liquid drop cooling Download PDFInfo
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- 239000007788 liquid Substances 0.000 title claims abstract description 46
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 9
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/42—Low-temperature sample treatment, e.g. cryofixation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N25/00—Investigating or analyzing materials by the use of thermal means
- G01N25/02—Investigating or analyzing materials by the use of thermal means by investigating changes of state or changes of phase; by investigating sintering
- G01N25/12—Investigating or analyzing materials by the use of thermal means by investigating changes of state or changes of phase; by investigating sintering of critical point; of other phase change
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Abstract
The application discloses a device for realizing high-speed cooling of trace materials by utilizing liquid drop cooling, which comprises: the injector is connected with the injection driver and is used for dripping volatile cooling liquid; a temperature sensor disposed directly below the injector; the data acquisition device is used for acquiring thermopile signals and heating resistor signals of the temperature sensor; the gas purging device is used for completing the cooled sample purging device; and the injector, the temperature sensor, the data acquisition device and the gas purging device are all connected with the control center. The device disclosed by the application can reach a cooling rate higher than that of common gas cooling by contacting a sample with the coolant liquid drops and controlling the heater to be turned off in a quick response manner through a program; simultaneously, the speed of cooling can be tracked by collecting thermopile signals or heating resistor signals, and the phase transition of a sample can occur; the volatile liquid is used, and after the cooling liquid drops are removed through gas purging, the next heat treatment or morphology characterization can be performed in situ.
Description
Technical Field
The invention relates to the technical field of acquisition and analysis of material microstructures, in particular to a device and a method for realizing high-speed cooling by utilizing liquid drop cooling.
Background
The industry often quenches samples from a melt to a solid (e.g., injection molding, film blowing, etc.) at cooling rates above 1000K/s and materials with varying degrees of order and recombination structures, including some polymers, metals, blends, alloys, etc., can be formed in such a complex process. The rapid cooling process of a small amount of melt is also involved in the recently rapidly developed additive technology and the 3D printing technology, so that the rapid cooling process of industry is simulated experimentally, and it is very important to know the quenching process of trace materials (from nanograms to tens of micrograms), which can help us know what happens specifically in the materials in the rapid cooling process involved industrially, so that the future industrial production can be guided better.
Both metal and polymer are very important materials, requiring cooling rates that are not achievable by conventional means. By reducing the sample size, a controlled high-speed cooling can be achieved using gas cooling. ultra-Fast Scanning Calorimeter (FSC) is an excellent technical means for observing materials during high-speed temperature rise and drop. It can prepare the sample with accurate heat history, analyze it at very high scanning speed, and capture the structure snapshot of the tiny sample at different temperature or time by ultra-high speed scanning (usually 100000K/s). However, rapid scanning of FSC also has its limitations, in particular the requirement for sample quality and the impact on scan rate when the sample temperature reaches ambient temperature.
Because of the excellent thermal conductivity and heat capacity of the gas, the thermal inertia is low, and air cooling is very effective when the sample needs to be rapidly switched from heating to cooling. But also because of these gas properties, the cooling efficiency is very significantly limited when the temperature difference between the sample and the gas approaches zero. In practice, FSC sensors can achieve a cooling rate of 10 6 K/s only when the temperature is higher than 500K, and only 1000K/s when the temperature is higher than 100K, and only 100K/s when the temperature is higher than 50K. When the temperature drops below a certain value, the cooling rate drops sharply, a phenomenon known as ballistic cooling (as shown in fig. 1), and the effect of ballistic cooling is particularly pronounced especially for samples of large mass. Ballistic cooling can be significantly reduced if helium is substituted for air, or experiments can be performed by reducing the gas temperature so as to avoid ballistic cooling at a specific temperature, say in liquid nitrogen cooled air or helium. However, this method is not always possible and is subject to the experimental platform and test conditions.
Disclosure of Invention
The application aims to: aiming at the defects in the prior art, the application provides a high-speed cooling device which replaces gas cooling with liquid cooling and achieves higher cooling rate, and provides a method for realizing high-speed cooling by using the device.
The technical scheme is as follows: the invention relates to a device for realizing high-speed cooling of trace materials by utilizing liquid drop cooling, which comprises: the injector is connected with the injection driver and is used for dripping volatile cooling liquid; the temperature sensor arranged right below the injector comprises a cold end and a hot end of the thermopile, a heating resistor is arranged in the thermopile, a silicon nitride film is attached to the surface of the thermopile, and trace materials are arranged on the silicon nitride film; the data acquisition device is used for acquiring thermopile signals and heating resistor signals of the temperature sensor; a gas purging device; and the injector, the temperature sensor, the data acquisition device and the gas purging device are all connected with the control center.
Wherein the device requires control of the size and flow rate of the cooling droplets by the injection driver and the injector, ensuring that the cooling droplets first contact the surface of the sample instead of the thin film of the sensor, in which case the cooling efficiency is the highest.
The syringe used to inject the droplets may be any device that can cause the liquid to form a steady stream or droplets, such as medical syringes and conventional PE droppers. Other injection devices, such as microfluidic devices, etc., are also possible. It should be noted that the diameter of the droplet needs to be larger than the diameter of the sample, the larger the diameter of the droplet, the higher the cooling efficiency. In general, droplets having a diameter of about 2mm can be cooled at a high rate.
Further, the cooling liquid is a liquid with certain volatility, and can be purged by a dry air flow after the sample is cooled, so that the cooling liquid drops are removed at the ambient temperature without changing the thermal history of the sample. Due to the leidenfrost effect, too fast evaporation of the liquid can cause it to boil on the hot sensor, thereby affecting the efficiency of cooling, even interrupting the cooling; in addition, when the test areas of the sensors are different, the boiling conditions of the cooling liquid drops are different, so that different properties of the cooling liquid are required to be selected according to the sensors with different areas.
Preferably, the cooling liquid is cold ethanol and the temperature is in the range of-50 ℃ to 0 ℃. Preferably at-20 ℃.
Any sample that does not dissolve or absorb the cooling liquid may be used in the device, and the diameter of the sample may vary from a few micrometers to hundreds of micrometers depending on the heating area of the temperature sensor used.
The temperature sensor is any currently available commercial vacuum gauge film sensor (xensor. Nl), such as XI394, XI395, and XI400, etc. Further, the XI394 measuring area used in the application is 8×6 μm 2, the XI395 measuring area is 60×60 μm 2, and the XI400 measuring area diameter is 500 μm.
The heating resistor on the sensor can preheat the sample to a certain designated temperature before cooling according to the requirement, and the heating range of the sample on the gold sensor is 0-1300K and the heating range of the aluminum sensor is 0-800K due to the voltage required by heating and the limitation of the heating resistor material on the sensor.
The purge gas flow of the gas purge device may 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.
The whole cooling process of the device is adopted, and the cooling rate is more than 10 6 K/s, so that the whole cooling process from the approach of liquid drops to the completion of cooling can be completed within 10 ms.
An improved rapid scanning calorimeter is integrated with the device for realizing the high-speed cooling of trace materials by utilizing liquid drop cooling.
Furthermore, the device for realizing the high-speed cooling of the trace materials by utilizing the liquid drop cooling is attached to a sample chamber of a rapid scanning calorimeter, comprises a room-temperature open platform, a cold and hot platform, a vacuum tube and the like, effectively realizes the further improvement of the cooling rate, and does not influence the further rapid thermal analysis and structural analysis.
The rapid scanning calorimeter can be a currently available FSC device, for example, fitting stacking can be performed for an open room temperature system, a cold and hot bench type closed system and a Tube-dewar type.
A method for realizing high-speed cooling of trace materials by using the device comprises the following steps:
(1) Sample preheating: placing a sample on a silicon nitride film of a temperature sensor, and preheating the sample to a specified temperature by using a heating resistor on the temperature sensor;
(2) High-speed cooling and data acquisition: dropping or spraying cooling liquid in the form of liquid drops onto the surface of the sample preheated in the step (1) through an injector, tracking the change of a thermopile signal in the process of approaching the liquid drops through a data acquisition device, when the liquid drops approach the sample, starting to reduce the temperature of the sample, deviating the thermopile signal for tracking the temperature of the sample from the designated temperature set in the step (1), and triggering to close a heating resistor when the reduced temperature difference delta T of the sample is larger than a preset trigger value delta T trigger; meanwhile, the temperature of the sample is continuously monitored with microsecond precision, the cooling rate and the possible phase transition of the sample are monitored, data are collected, and the subsequent data analysis is carried out;
(3) And (3) drying a sample: after the cooling is completed according to the acquired data in the step (2), a gas purging device is started by a control center to remove cooling liquid drops, and the sample without liquid drop residues can be subjected to rapid thermal analysis or structural analysis of sample materials in situ to complete high-speed cooling.
The specified temperature in the step (1) needs to be set specifically according to experimental requirements, and the specified temperature of the sample can be generally in the maximum range of 100K-800K. The maximum temperature range of the sample may be 100K-1300K when using gold sensors.
In step (2), the internal triggering process controlled by the data collector can be implemented in microseconds, which can track the approach of the droplet before it touches the sample, and shut down the temperature control system for the sample (i.e. the heating resistor) to achieve the optimal cooling rate when needed, which can be affected either too early or too late. The temperature of the sample is monitored continuously with microsecond precision in the cooling process, and the temperature signal can display the cooling rate and the possible phase transition of the sample.
Since the reference temperature at the cold end is ambient, when the reference temperature of the thermopile signal (cold end) is unreliable, say when the drop temperature is much lower than the temperature of the sensor, the temperature measurement and correction can be performed using the existing heating resistor on the sensor.
The temperature of the cooling liquid drops is lower than the temperature of the preheated sample, and the contact of the liquid drops and the closing of the heater can realize the rapid cooling of the sample.
Any sample that does not dissolve or absorb the cooling liquid in step (1) may be used in the device, and the diameter of the sample may vary from a few micrometers to hundreds of micrometers depending on the heating area of the temperature sensor used.
In step (2), the cooling liquid is cold ethanol at a temperature in the range of-50 ℃ to 0 ℃, preferably-20 ℃.
In step (3), the sample is cooled and then purged by a dry gas stream 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 freely set. A purge of 1L/min for 30s may be selected for ethanol. After rapid cooling, the sample can be subjected to rapid thermal analysis in situ, including re-heating to analyze the structure of the cooled sample, or further heat treatment, such as isothermal or non-isothermal experiments; other morphological or mechanical characterization can also be performed without transfer to other equipment.
The beneficial effects are that: according to the high-speed cooling device, the cooling rate higher than that of common gas cooling can be achieved through the contact of the coolant liquid drops with the sample and the program control of the quick response closing of the heater; simultaneously, the speed of cooling can be tracked by collecting thermopile signals or heating resistor signals, and the phase transition of a sample can occur; the volatile liquid is used, and after the cooling liquid drops are removed through gas purging, the next heat treatment or morphology characterization can be performed in situ. The high-speed cooling method can be used for obtaining special phases of sample materials, can be combined with the existing ultra-fast scanning calorimetric technique, expands the high-speed cooling rate of a trace sample, realizes the simulation of an industrial quenching process, and simultaneously carries out in-situ thermal analysis and microstructure characterization on the materials obtained by high-speed cooling.
For example, for some technical grade resins (e.g., homogeneously nucleated polyethylene PE or polytetrafluoroethylene PTFE) that crystallize very rapidly, even samples of very small mass are cooled with gas and the cooling rate is not satisfactory, whereas the crystallization rate of the metallic material is faster. In this case, additional liquid cooling would be greatly helpful. The method for realizing high-speed cooling by utilizing liquid drop cooling can be combined with the existing rapid scanning calorimeter, realizes high-speed cooling and subsequent calorimetric characterization and other microstructure characterization according to different cooling rate requirements, use environments and instrument combination conditions, and can help to more comprehensively explain the influence of rapid cooling and the performance of the plastic or metal alloy product prepared after rapid cooling by obtaining the complementary information. The use of liquid for additional cooling can greatly extend the limitations of conventional FSCs, while also making them a very commercially attractive instrument.
Drawings
FIG. 1 is a schematic diagram of ballistic cooling;
FIG. 2 is a basic structural schematic diagram of a device for realizing high-speed cooling of trace materials by using liquid drop cooling;
FIG. 3 is a schematic view of the structure of the device of the present application;
FIG. 4 is a detailed schematic diagram of the cooling process;
FIG. 5 is a schematic diagram of the liquid cooling principle of operation;
FIG. 6 is a schematic diagram of the step 2 trigger off heating resistor process of the present application;
FIG. 7 is a schematic diagram of the liquid cooling device in combination with an existing fast scanning calorimeter FSC;
FIG. 8 is a schematic diagram of a comparison of a gas cooled FSC device of the type tube-dewar and a combination of a liquid cooled device and a tube-dewar FSC device;
FIG. 9 is a graph comparing the liquid cooling effect of the present application with the conventional gas cooling effect;
FIG. 10 is a graph comparing cooling effects on sensors of different area sizes using cold ethanol as the cooling liquid, with lower sensor area, less liquid boiling, and higher cooling rates achievable.
Detailed Description
The present application will be described in detail with reference to specific examples.
Example 1
The device for realizing high-speed cooling of trace materials by using liquid drop cooling as shown in fig. 2 and 3 comprises: an injector connected to the injection driver for dripping the volatile cooling liquid; the temperature sensor arranged right below the injector comprises a cold end and a hot end of the thermopile, a heating resistor is arranged in the thermopile, a silicon nitride film is attached to the surface of the thermopile, and trace materials are arranged on the silicon nitride film; the data acquisition device is used for acquiring thermopile signals and heating resistor signals of the temperature sensor; the gas purging device is used for purging the cooled sample; and the injector, the temperature sensor, the data acquisition device and the gas purging device are electrically connected with the control center.
Example 2
The method for realizing high-speed cooling of the trace material by using the device in the embodiment 1 is shown in fig. 4, and comprises the following steps:
(1) Sample preheating: placing a sample on a silicon nitride film of a temperature sensor, and preheating the sample to a specified temperature by using a heating resistor on the temperature sensor;
(2) High-speed cooling and data acquisition: dropping or spraying cooling liquid in the form of liquid drops onto the surface of the sample preheated in the step (1) through an injector, tracking the change of a thermopile signal in the process of approaching the liquid drops through a data acquisition device, wherein as shown in fig. 5 and 6, when the liquid drops approach the sample, the temperature of the sample starts to be reduced, the thermopile signal for tracking the temperature of the sample deviates from the designated temperature set in the step (1), and when the reduced temperature difference delta T of the sample is larger than a preset trigger value delta T trigger, the heating resistor is triggered to be turned off; meanwhile, the temperature of the sample is continuously monitored with microsecond precision, the cooling rate and the possible phase transition of the sample are monitored, data are collected, and the subsequent data analysis is carried out;
(3) And (3) drying a sample: after the acquired data in the step (2) shows that cooling is finished, a gas purging device is started by a control center to remove cooling liquid drops at the ambient temperature, so that a sample without liquid drop residues can be subjected to rapid thermal analysis or structural analysis of a sample material in situ, and high-speed cooling is finished.
Wherein, in the step (2), the cooling liquid is cold ethanol with the temperature range of minus 20 ℃; in the step (1), the designated temperature range is 100K-800K, and the maximum temperature range of the sample can be 100K-1300K when the gold sensor is used. ; in the step (3), the gas purging device purges 30s at a purging gas flow rate of 1L/min.
Comparative example 1
The cooling operation was performed under the same conditions using the apparatus shown in example 1 and the conventional gas cooling apparatus, and as a result, as shown in fig. 9, it was seen from the graph that the drop cooling (solid black line) was significantly superior to the rate-of-decrease performance of the atmosphere cooling (broken gray line). Linear coordinates-a, double logarithmic coordinates-b.
Comparative example 2
We performed comparative experiments of the liquid and gas cooling performance using the apparatus of example 1 on several different gauges of sensors including XI394 (measurement area 8x6 μm 2), XI395 (measurement area 60x60 μm 2) and XI400 (measurement area diameter 500 μm), the test results being shown in fig. 10, the comparative data being shown in the table below, whereby boiling of cold ethanol on the XI400 sensor (UHC-1 Flash DSC sensor, diameter 500 μm,2 μm thick) reduced the liquid cooling performance (grey curve) but was still much better than the original slow cooling (black curve). The gray curve is the result of either liquid cooling (gray dotted line) or conventional cooling (black dotted line) on an XI395 sensor (60 x80 μm 2, 1 μm thick) at the same temperature. Therefore, the sensor area has a larger influence on the cooling effect, and the larger the sensor area is, the more serious the boiling phenomenon of the cooling liquid is, and the lower the cooling rate is. However, even for the XI400 sensor with the largest test area, the cooling rate achieved with the additional droplet cooling is much better than that achieved with the conventional gas cooling.
Example 3
As shown in FIG. 8, a Tube-dewar type fast scanning calorimeter FSC integrated with the device described in example 1, the sample compartment of the device of example 1 is placed in a vacuum Tube in a Dewar flask, the basic schematic diagram of which is shown in FIG. 7, since the furnace with the sensor can be kept at a very low temperature (about 80K), the usable temperature range and scanning rate can be greatly increased, and the fastest cooling rate of the current fast scanning calorimeter can be achieved by adding an additional liquid drop cooling device.
Claims (7)
1. A device for realizing high-speed cooling of trace materials by utilizing liquid drop cooling, which is characterized in that the cooling rate of the high-speed cooling is more than 10 6 K/s, and the device comprises:
the injector is connected with the injection driver and is used for dripping volatile cooling liquid;
the temperature sensor arranged right below the injector comprises a cold end and a hot end of the thermopile, a heating resistor is arranged in the thermopile, a silicon nitride film is attached to the surface of the thermopile, and trace materials are arranged on the silicon nitride film;
the data acquisition device is used for acquiring thermopile signals and heating resistor signals of the temperature sensor;
the gas purging device is used for purging the cooled sample to remove cooling liquid drops;
a trigger for triggering the heating resistor to be turned off;
And the injector, the temperature sensor, the data acquisition device and the gas purging device are electrically connected with the control center.
2. An improved rapid scanning calorimeter which is characterized in that the device for realizing the rapid cooling of trace materials by utilizing liquid drop cooling is integrated.
3. The improved rapid scanning calorimeter of claim 2, wherein the means for achieving rapid cooling of the trace material using drop cooling is integrated into the sample chamber of the rapid scanning calorimeter.
4. A method for realizing high-speed cooling of trace materials by using the device of claim 1, which is characterized by comprising the following steps:
(1) Sample preheating: placing a sample on a silicon nitride film of a temperature sensor, and preheating the sample to a specified temperature by using a heating resistor on the temperature sensor;
(2) High-speed cooling and data acquisition: dropping or spraying cooling liquid in the form of liquid drops onto the surface of the sample preheated in the step (1) through an injector, tracking the change of a thermopile signal in the process of approaching the liquid drops through a data acquisition device, when the liquid drops approach the sample, starting to reduce the temperature of the sample, deviating the thermopile signal for tracking the temperature of the sample from the designated temperature set in the step (1), and triggering to close a heating resistor when the reduced temperature difference delta T of the sample is larger than a preset trigger value delta T trigger; meanwhile, the temperature of the sample is continuously monitored with microsecond precision, the cooling rate and the possible phase transition of the sample are monitored, data are collected, and the subsequent data analysis is carried out;
(3) And (3) drying a sample: after the acquired data in the step (2) shows that cooling is finished, a gas purging device is started by a control center to remove cooling liquid drops at the ambient temperature, so that a sample without liquid drop residues can be subjected to rapid thermal analysis or structural analysis of a sample material in situ, and cooling is finished.
5. The method of claim 4, wherein in step (2), the cooling liquid is cold ethanol having a temperature in the range of-50 ℃ to 0 ℃.
6. The method of claim 4, wherein in step (1), the specified temperature range is 100K-800K.
7. The method of claim 4, wherein in step (3), the gas purge gas flow is 0-10L/min.
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