Certain examples of the technology described herein relates to the field of phase and microstructure analysis. Specifically, it is a stage-type fast scanning calorimetry which can be integrated with other structure characterization approaches, in order to perform in-situ microstructure detection to the sample after fast heat treatment.
Metastable or transient state materials usually exhibit fantastic physical chemical properties, and many materials with excellent performance are in special metastable states. For example, we usually quench the steels to transit it from austenite to metastable martensite, in order to improve the functional performance Research on metastable materials have been one of the hotspots, it involves various field including materials science, physics, chemistry, biology, power, medicine, food, environment, etc. The simplest and most direct way to obtain metastable states is heat treatment. As a result, thermal analysis, especially fast thermal analysis has been the most effective and reliable approach to study metastable materials.
In recent years, Christoph Schick and co-workers built the first fast scanning calorimeter (FSC, Patent Number: US20100046573A1) using commercial thin film vacuum sensor (thermal conductivity gauge, TCG-3880, Xensor Integration, NL), the controlled heating and cooling rate was 1 to 10000 K/s (Kelvin per second) or even higher. Specifically, the sample is cut into nanogram to microgram and transferred onto the film sensor. By which means the thermal capacities of the sample and addenda are significantly reduced, so that the heating and cooling rate could be increased. Using this method, they successfully studied the melting-recrystallizing-remelting processes of many polymers such as poly(dimethyl phthalate), polypropylene, polyamide blends, isotactic polystyrene and so on. Under such high heating and cooling rate, some structural transition could be restrained. Fast scanning calorimetry, therefore, can be applied in studying the thermal properties of some metastable materials. And besides, we can obtain the metastable states by fast heat treatment using FSC. However, the information provided only by FSC cannot meet the requirements of research on the structures and properties of metastable materials. As a results, it is necessary to develop a technique to integrate fast thermal analysis with structure characterization approaches in order to obtain the structural information of sample under metastable states.
There are two difficulties, though, to realize the technique above: 1. The working space of most structure characterization equipment are relatively small, while the available FSC takes tube-dewar method to control the temperature of sample chamber, which is difficult to in-situ integrate with other equipment. We have to transfer the sample into other equipment if we want to perform structural characterization of the metastable sample after fast heat treatment. But the structure of the sample has probably changed after this process. 2. As the heat capacities of the sample and addenda are small for FSC, the illumination of incoming light will cause great effect to the sample temperature. Unfortunately, the available FSC controls the temperature of sample by power compensation. Which means, if the effect of light illumination to the sample temperature exceeds the limit of power compensation, FSC will lose control of the sample temperature and the sample's structure may change, as well.
In order to overcome these difficulties, a stage-type fast scanning calorimetry (ST-FSC) is invented. Besides the FSC's capability, it has the following characteristics: 1. There are transmission and reflection windows on the opposite sides of the sealed sample chamber, and a thermal stage in the chamber containing heating components, pipes for coolant and a hole for light transmission inside the stage. 2. The ST-FSC can perform fast response and adjustment to the temperature change of sample. The way to control the temperature of sample is changed to fast monitoring it directly by computer program, in order to guarantee the temperature of sample at the setpoint, and prevent the effect of light illumination from structure characterization equipment. 3. The ST-FSC can meet the requirements to detect both transmission and reflection signals, therefore it can be integrated with various structure characterization equipment.
A stage-type fast scanning calorimetry is provided. In certain examples, it comprises sample chamber (100), temperature control system (400) of sample chamber and fast calorimetric system (200).
The sample chamber (100) comprises: a thermal stage (110) with heating components, pipes for coolant and transmission hole (109) inside, reflection window (107), transmission window (108), wiring terminals (101) for film sensors, signal plug (102) for film sensors, inlet (103) for coolant, outlet (104) for coolant, signal plug (105) for temperature control of the thermal stage, and atmosphere channel (106). The refection and transmission windows are on the opposite sides of the sealed sample chamber.
The reflection window (107) allows the incidence light to illuminate onto the sample and the reflected light to exit the chamber. Transmission window (108) allows the incidence light to illuminate onto the sample through the transmission hole (109), and to exit through the reflection window (107). The selection of reflection window (107) and transmission window (108)'s transparent materials are according to the application, calcium fluoride lenses, for example, are recommended to use in ultraviolet, visible and infrared optical detection, while for the detection relative to X-ray the polyimide film lenses may be a good choice.
The thermal stage (110) provides the ambient temperature for the sample. The surface of the stage is made of silver or other materials with good heat conduction, in order to keep the temperature uniformity of the surface. There are temperature sensors, heating elements and pipes for coolant (like liquid nitrogen or so) inside the thermal stage (110). The inlet (103) and outlet (104) for the coolant allow the coolant enter into the inner loop of the thermal stage. The transmission hole (109) is throughout the thermal stage, facing the reflection (107) and transmission (108) windows, so that the light can pass though the stage and illuminate onto the sample. The wiring terminals (101) for film sensors connect the signal wires of the sensors to the signal plug (102). The signal plug (105) for temperature control of the thermal stage connect to temperature control system (400) of sample chamber, in order to make the temperature of the stage under control. The atmosphere channel (106) allows the atmosphere connection inside and outside of the chamber.
The temperature control system (400) of sample chamber can heat as well as cool the thermal stage, so that the temperature of stage's surface could be hold to a very setpoint.
The fast calorimetric system (200) comprises: reference film sensor (220), film sensor for loading sample (210), fast temperature control and measurement system (300) and computer for program control and data processing (500).
The reference film sensor (220) and film sensor for loading sample (210) should include thermocouples or thermopiles and heating resistance to measure and control the temperature. In certain embodiments, the commercial thermal conductivity gauge model XEN-39391, XEN-39392, XEN-39394, XEN-39395 or so loading on the XEN-014 ceramic substrates from Xensor Integration could be used as the sensors.
The fast temperature control and measurement system (300) comprises: PID controller (310) to receive temperature signals from reference film sensor (220) and produce control signals, differential amplifier (320) to receive temperature signals from both reference sensor (220) and sample sensor (210) in order to produce control signals, and fast digital-analog converter to output and gathering signals (not marked in figures, integrated with the computer). The controller (310) provides an average power for sample sensor (210) and reference sensor (220) according to the received temperature signals. The differential amplifier (320) provides compensation power for the sample sensor (210) according to the received temperature signals of sample sensor (210) and reference sensor (220). In certain embodiments, the fast digital-analog converter has 1 digital to analog conversion interface and 8 analog to digital conversion interfaces. And different sampling rate and precision are adopted to the requirement. In certain embodiments, the sampling rate of asynchronous 1.25 MS/s and accuracy of 16 bit or above are preferred. Besides, the converter should have appropriate input and output buffer to match the sampling rate. According to the heating and cooling rates, the computer (500) write the temperature program into output buffer, and provide the signal to the setpoint interface of controller (310) after digital-analog conversion. The measuring interface of controller (310) is connected to the thermopiles of reference sensor (220). The controller (310) provides an average heating power to both reference sensor (220) and sample sensor (210) according to the signals from setpoint and measuring interfaces. In certain embodiments, the differential amplifier (320) is an integrated operational amplifier circuit of adder or subtractor, also can be a PID controller. It provides compensation power to sample sensor (210) according to the temperature signals from thermopiles of sample sensor (210) and reference sensor (220).
The certain examples described herein could perform thermal analysis at the heating and cooling rates up to 200,000 K/s. The metastable states of most samples, especially the polymers, can be captured at this scanning rates. The ST-FSC can perform in situ spectroscopic detection to obtain the microstructural information of the sample through the transmission window (107), reflection window (108) and transmission hole (109), after the metastable states are captured. Meanwhile, the temperature of sample is stable at the setpoint by millisecond-time-period program control loop, to prevent the structural transition induced by the illumination of light. The above work cannot be accomplished in other similar equipment (such as the fast scanning calorimetry described in patent US20100046573A1).
Additional features, aspects, examples and embodiments are described in more detail below.
Additionally in
The block diagram of certain embodiments described herein is shown in
There are built-in measuring and heating elements in the thermal stage (110). The temperature control system of sample chamber (400) acquires the temperature of the thermal stage (110) through the interface (105), and provides heating and cooling signals, accordingly. The heating signals applies on the heating elements in thermal stage through the interface (105), while the cooling signals control the external liquid nitrogen pump or magnetic valve to import the coolant into the thermal stage through inlet (103), and drained from outlet (104) after the circulation inside the thermal stage. By this means, the temperature of thermal stage (110) can be controlled by the temperature control system (400). In addition, 106 is a channel to control the atmosphere in the sample chamber in case the atmosphere affects the sample.
Each of the film sensors (210 or 220, shown in
The PID controller (310, shown in
As shown in
According to the arrangement shown in
In order to avoid the incident light affecting the temperature of sample, the computer (500) detects the sample temperature in real time, which can be calculated from the signals obtained by fast temperature control and measurement system (300). And meanwhile, the temperature of sample is stable at the setpoint by millisecond-time-period program control loop. An experiment was performed to verify effect of this method. A small piece of polyethylene terephthalate was taken as sample, and illuminated by a laser source with a power of 6 mW and wavelength of 785 nm. The temperature of sample was detected during turning on and off the laser source, as shown in
In addition, in order to ensure the reliability of results when the ST-FSC is integrated with microstructure characterization equipment, the following experimental scheme is suggested. First, to obtain the desired state of samples by thermal treatment of ST-FSC using a specific temperature program. Second, to quench the sample to the temperature far below the one that may induce the structural transition of the sample and hold, the cooling rate should be high enough to suppress any structural transition. Third, to characterize the samples structure by the integrated equipment.
The detailed description above is not the limitations, but only used to illustrate a certain example of this invention. Ordinary technicists in relative technical fields can also make various changes under this description. So all the equivalent technical proposals also belong to the scope of the invention.
Number | Date | Country | Kind |
---|---|---|---|
201310499799.9 | Oct 2013 | CN | national |
Filing Document | Filing Date | Country | Kind |
---|---|---|---|
PCT/CN2013/090170 | 12/20/2013 | WO | 00 |