CN104569047A - Adiabatic following device for solid specific heat capacity measurement standard device - Google Patents
Adiabatic following device for solid specific heat capacity measurement standard device Download PDFInfo
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Abstract
The invention belongs to the field of measuring science, and relates to an adiabatic following device for a solid specific heat capacity measurement standard device. The adiabatic following device sequentially comprises a Dewar (21), a tracking screen (22), a heat insulation screen (23) and a shell (4) from inside to outside, wherein the Dewar (21) consists of a bottle body and a bottle cap which are respectively made of high-temperature-resistant double-layer quartz glass; the tracking screen (22) is made of red copper; the bottom of the Dewar is provided with a flaky ceramic heater (221) and a working temperature sensor (222); the heat insulation screen (23) is made of stainless steel and has a multilayered structure; the shell (24) is made of stainless steel and consists of a shell body and a shell bottom which are connected with each other by a vacuum sealing flange; a vacuum high-density connector, a high-precision pressure sensor and an air charging and discharging interface are arranged on the shell bottom. After the adiabatic following device is used, the problem of temperature gradient is solved, and the high adiabaticity of a sample container of the solid specific heat capacity measurement standard device is guaranteed, so that the solid specific heat capacity is accurately measured.
Description
Technical field
The invention belongs to field of metrology science, relate to a kind of specific heat of solid and heat metrological standard unit of measuring for specific heat of solid and heat and the sampling receptacle that comprises of this device and adiabatic tracking means, and adopt the measuring method of this specific heat of solid and heat metrological standard unit.
Background technology
Specific heat capacity (abbreviation thermal capacitance) is one of hot physical property of material, by the measurement of thermal capacitance, the Basic thermodynamics data such as enthalpy, entropy, Gibbs free energy can be obtained on the one hand, the important information of the aspect such as structure, phase transformation of related substance can also be obtained on the other hand.The assay method of thermal capacitance is divided into absolute method and relative method, and relative method mainly comprises DSC, DTA etc., and its precision and accuracy are well below absolute method.Can find out that the thermodynamic data measurement of relative method needs by one-level α-Al from China's thermal capacity value traceability system (as shown in Figure 1)
2o
3molar heat capacity standard substance is calibrated, and guarantee value accurately and reliably.Standard substance wherein as magnitude tracing carrier realizes effectively measurement and basic assurance that is accurate, comparable, that can trace to the source, and the source that disjunction mark standard is standard substance magnitude tracing is measured by country, is the key problem ensureing magnitude tracing.The national measurement institute of various countries, in order to trade development, standard market order, Promote Technology, improves constantly the measurement level of national disjunction mark standard apparatus, develops relevant standard substance to remain on the superiority in fierce market competition.Current China one-level α-Al
2o
3molar heat capacity standard substance and one-level thermal analyses standard substance lack metrological standard unit definite value, original primary standard amount of material is limited, as highest level metering mechanism of country, setting up specific heat of solid and heat metrological standard unit is standard substance definite value, thus promote the measurement level of national thermodynamics measurement data, ensure the accurate of China's measurement of correlation analytical instrument measurement data, simultaneously also for the standard substance opening up more wide temperature range lays a good foundation, therefore, the work of setting up specific heat of solid and heat metrological standard unit is extremely urgent.
Specific heat of solid and heat measurement mechanism is divided into two types by type of heating difference: a kind of for being interrupted hot type, one is laser heating type.For mesophilic range, the general type of heating adopting discontinuous.Heating continuously or to be interrupted be come as required to be regulated by controller to realize.In whole temperature range, often raise 5 degree or 10 degree, stopping heating, enters balance period, after reaching equilibrium condition, continues heating, and Here it is, and alleged discontinuous heats.
For developing the thermal capacitance measurement mechanism of high precision high accuracy, need to develop a set of adiabatic calorimeter device, and the most crucial part of device be sampling receptacle design, follow the tracks of screen and insulated design.Wherein, sampling receptacle has the effect holding sample, settle well heater and maintenance uniform temperature fields.Tracking screen and insulated design are then round the three kinds of approach suppressing, isolate heat loss.Heat loss has three kinds of approach, convection current, conduction and radiation, and tracking screen and insulated design need to launch around this three approach.
Zhang Jintao etc. propose a kind of High Precision Automatic Adiabatic Calorimeter to standard substance α-Al
2o
3carried out specific heat measurement (" High Precision Automatic Adiabatic Calorimeter ", metering journal, Vol.26, No.4, in October, 2005,320-325), this instructions introduced by this section of document, as a reference.The Automatic Adiabatic calorimeter structure of its report is as follows: sampling receptacle is the cylindrical closed vessel of thin-walled, volume is about 60ml, outside surface is gold-plated to reduce radiation heat transfer, the soldering of sampling receptacle mouth seals, inner air is extracted out after sealing, be filled with helium, and the helium be filled with is sealed in sampling receptacle, to strengthen the convective heat exchange between sample and sample heating device; Have the heat radiation screen can following the tracks of sample temperature outside sampling receptacle, the system that sampling receptacle and heat radiation screen are formed is placed in a vacuum interlayer, and vacuum interlayer is soaked in liquid nitrogen, and therefore, heat radiation screen is placed between sampling receptacle and the environment of liquid nitrogen temperature; Heat radiation screen outside surface is furnished with heater strip equably, and there is thermoelectricity to push away between sampling receptacle, the end of probe that thermoelectricity pushes away and reference edge are connected on the inwall of sampling receptacle outer wall and heat radiation screen, its electric potential difference signal is admitted to controller, the feedback adjustment signal of controller controls heat radiation screen heater power source, and electric potential difference signal is gone to zero all the time.Therefore, by such temperature controlling and regulating system, the temperature of heat radiation screen is controlled all the time, makes it follow the tracks of the wall surface temperature of sampling receptacle.The defect that this adiabatic calorimeter exists is mainly: (1) sampling receptacle mouth seals with soldering at every turn, do the measurement directly having influence on sampling receptacle space amount like this, this process itself does not have very strong repeatability, the uncertainty introduced is larger, meanwhile, soldering also easy damage device being caused to unrepairable is repeated; (2) such design is in the use of sampling receptacle, very uneconomic, because welding quality has higher requirements in processing technology, require that weld seam can tolerate vacuum, if vacuum tightness is bad, inert gas then in sampling receptacle leaks in the situation of being heated, thus affects the accuracy of measurement result; (3) Zhang Jintao etc. adopt this adiabatic calorimeter to α-Al in the temperature range of 80 ~ 275K
2o
3carry out calorimetric experiment.
Chinese patent 200810010885.8 discloses a kind of Calorimetry system, and this instructions introduced by this section of patent documentation, as a reference.Wherein, disclosed adiabatic calorimeter adopts three layers of heat screen temperature control to keep adiabatic environment, sampling receptacle is made up of upper cover and main body, the lateral margin of the upper end outer wall of main body is provided with sealing the margin, upper cover is fastened on blend compounds adhesive seal on sealing the margin and connects, on cover and be connected with kapillary and link, heater strip is wound on the outer wall of main body, heat radiator, thermometer and differential thermopair is provided with in main body, sampling receptacle hangs in interior heat screen by link, and kapillary is used for sampling receptacle and fills helium.Also there is above-mentioned similar problem in this Calorimetry system, is in fact all to leave for from a some problem solving heat interchange.But from a device, it should be reused, and each error using generation is within the specific limits, is one and determines state.So will take into full account reusing of device in design, meanwhile, the space amount for sampling receptacle and device all can Measurement accuracy, so just can reduce the error of device to greatest extent.
Above-mentioned adiabatic calorimeter have employed one deck heat radiation screen or three layers of heat screen in adiabatic tracking means design, but avoid a very important problem-thermograde, namely directly there is thermograde in sampling receptacle internal heater and sampling receptacle, directly also there is thermograde in sampling receptacle upper and lower, this problem equally also exists on tracking screen, due to the existence of thermograde, follow the tracks of temperature and there will be error, also be difficult to the exchange heat avoided sampling receptacle and follow the tracks of between screen, be so just difficult to the strict energy confirming to inject sampling receptacle.
Existing adiabatic calorimeter major part is measured warm area and is also confined to below 350K, few more than the calorimeter of 400K warm area.This is mainly because of the rising along with temperature, the heat interchange that the heat interchange caused by radiant heat transfer causes than convection current and conduction is much bigger, increase for realizing adiabatic difficulty, the thermal capacitance measuring error of measured matter is strengthened, simultaneously, at a higher temperature, the Insulation Problems of the sealing of sample, heater strip and lead-in wire highlights.
Therefore, for adiabatic calorimeter, the high thermal insulation of sampling receptacle guaranteed by the adiabatic tracking means of more scientific reasonable design and sampling receptacle, scientific design fills emission control automatically to realize easy and simple to handle and robotization, thus measure specific heat of solid and heat more exactly, realizing specific heat capacity measurement data traces to the source to international SI unit, there are needs on the one hand at this.
Summary of the invention
Technical matters
In order to solve the problem, one object of the present invention is to provide a kind of sampling receptacle for specific heat of solid and heat metrological standard unit, this sampling receptacle passes through appropriate design, the whole sampling receptacle homogeneous temperature when measuring, and without the need to sealing with soldering and being glued sealing.
Another object of the present invention is to provide a kind of adiabatic tracking means for specific heat of solid and heat metrological standard unit, this adiabatic tracking means solves the problem of thermograde, guarantees the high thermal insulation of sampling receptacle.
An also object of the present invention is to provide the specific heat of solid and heat metrological standard unit comprising above-mentioned sampling receptacle and adiabatic tracking means, this specific heat of solid and heat metrological standard unit can realize increasingly automated control without the need to too much manually on duty when measuring, and measures specific heat of solid and heat exactly.
Another object of the present invention is to provide the method adopting above-mentioned specific heat of solid and heat metrological standard unit accurately to measure specific heat of solid and heat.
Technical scheme
According to an aspect of the present invention, sampling receptacle 10 for specific heat of solid and heat metrological standard unit provided by the invention by the bottom of sample cell body 11, pond 12 and pond cover 13 and form, pond body 11 with at the bottom of pond 12 to coordinate be clearance fit, pond lid 13 is also clearance fit with coordinating of pond body 11; At least two auxiliary sheet ceramic heaters 14 are furnished with bottom described sample cell, at least two main leaf shape ceramic heaters 15 are symmetricly set in sample cell, a standard temperature sensor 17 is arranged on sample cell center, and at least two working temperature sensors 16 are arranged between flaky pottery well heater 15 and pool wall.
According to a further aspect of the invention, the adiabatic tracking means 20 for specific heat of solid and heat metrological standard unit provided by the invention, comprises Dewar flask 21 from inside to outside successively, follows the tracks of screen 22, thermoscreen 23 and housing 24.Wherein, described Dewar flask 21 is made up of bottle and bottle cap, and described bottle and bottle cap are made by high-temperature resistant double-layer quartz glass, be vacuum and have silver coating at double-deck inside quartz glass, and vacuum tightness is 10
-5~ 10
-6pa, the bottom of bottle is provided with wire hole, and hole is embedded with ceramic insulating tube;
It is outside that described tracking screen 22 is arranged on Dewar flask 21, is made up of red copper, and form by the bottom of the bottle of closure of openings and bottle, at least two flaky pottery well heaters 221 are equipped with at bottle base fabric, and be furnished with working temperature sensor 222, and be provided with wire hole at the bottom of bottle, hole is embedded with ceramic insulating tube;
Described thermoscreen 23 is arranged on that to follow the tracks of screen 22 outside, and being made up of stainless steel, is sandwich construction, and at the bottom of bottle, body and bottle cap stud be fixed as entirety, and be provided with wire hole at the bottom of bottle, hole is embedded with ceramic insulating tube;
It is outside that described housing 24 is arranged on thermoscreen 23, is made up, forms by the bottom of housing and shell of stainless steel, and housing is connected with employing vacuum seal flange at the bottom of shell, is provided with vacuum high-density connector, high-precision pressure sensor and fills exhaust port at the bottom of shell.
According to also one side of the present invention, specific heat of solid and heat metrological standard unit 100 provided by the invention comprises sampling receptacle 10, adiabatic tracking means 20, inflating and exhausting system 30 and Measurement and Control System 40, and wherein, sampling receptacle 10 is placed in adiabatic tracking means 20;
Described inflating and exhausting system 30 is for inflating to sampling receptacle 10 and adiabatic tracking means 20 and be vented;
Described Measurement and Control System 40 comprises: the sample heating system 42 heated for Quality control container 10; Examining system 41 is returned for measuring the sample heat energy injecting sample energy size; For the temperature measurement system 43 of the temperature real-time measurement of sampling receptacle 10 temperature and adiabatic tracking means 20; For the adiabatic tracking control system 44 that adiabatic tracking means 20 controls; And for the computing machine 45 of data acquisition and processing (DAP).
According to another aspect of the invention, the above-mentioned specific heat of solid and heat metrological standard unit of employing provided by the invention measures the method for specific heat of solid and heat, the method comprises: sampling receptacle 10 and adiabatic tracking means 20 are under inert gas atmosphere, measure the thermal capacitance of empty sampling receptacle 10, then the thermal capacitance being loaded with the sampling receptacle 10 of testing sample is measured, the molar heat capacity by following formula calculation sample:
In formula: m is the quality (g) of sample,
M is the molal weight (g/mol) of sample,
C
e, c
fbe respectively sky sampling receptacle, be loaded with the mean heat capacity (J/K) of the sampling receptacle of testing sample,
C
m(T) be the mean molal heat capacity (J/molK) of sample.
Beneficial effect
Specific heat of solid and heat metrological standard unit of the present invention, under when measuring, adiabatic tracking means and sampling receptacle are in identical inert atmosphere, without the need to sealing sampling receptacle with soldering or be glued, and by the distribution of flaky pottery well heater 14 and 15 in sampling receptacle, when measuring, whole sampling receptacle temperature is easy to even;
The problem that Dewar flask 21 solves thermograde is set in adiabatic tracking means 20, guarantees the high thermal insulation of sampling receptacle;
This specific heat of solid and heat metrological standard unit can realize increasingly automated control without the need to too much manually on duty when measuring, and measures specific heat of solid and heat exactly.
Accompanying drawing explanation
Tu1Shi China thermal capacity value traceability system schematic diagram;
Fig. 2 is the structural representation of sampling receptacle 10 of the present invention, and wherein (A) is the cut-open view along A-A line, and (B) is the structural representation of sampling receptacle 10, and (C) is the structural representation of at the bottom of sampling receptacle 10 pond 12;
Fig. 3 is the structural representation of adiabatic tracking means 20 of the present invention;
Fig. 4 is the structural representation automatically filling emission control 30 of the present invention;
Fig. 5 is the structural representation of specific heat of solid and heat metrological standard unit 100 of the present invention.
Embodiment
Below, more specifically the present invention is described by reference to the accompanying drawings.
According to sampling receptacle 10 of the present invention as shown in Figure 2, its by the bottom of pond body 11, pond 12 and pond cover and 13 to form, at the bottom of described pond body 11, pond 12 and pond lid 13 to make by fine silver, adopt fine silver material, mainly consider that the thermal conductivity of silver is very good, be seven times of steel, specific heat capacity is little, can ensure that the sample in sample cell is heated evenly like this, and heat absorption is relatively good; Described pond body 11 is 70ml ~ 100ml with 12 spatial volume formed at the bottom of pond, such as, can be 80ml; At the bottom of pond, the thickness of 12 is 8 ~ 14mm, such as, can be 12mm; The wall thickness of pond body 11 and Chi Gai is 2 ~ 5mm, such as, can be 3mm; Described sample cell can be square or cylindrical, and preferably cylindrical; Pond body 11 is with at the bottom of pond 12, and 13 coordinate and be clearance fit is covered in pond body 11 and pond.
At least two auxiliary sheet ceramic heaters 14 are furnished with bottom described sample cell, it can be such as the flaky pottery well heater 14 of at least two 2.7 ~ 3 ohm, 3 watts, and be preferably the round sheet ceramic heater 14 of three 3 ohm, 3 watts, around the distribution triangular in shape of sample cell bottom centre, the round sheet ceramic heater 14 of these 3 ohm, 3 watts is auxiliary heater, be used at the bottom of pond, heated sample pond, it is used as to compensate the temperature difference between the upper and lower differing heights of sample cell; At least two main leaf shape ceramic heaters 15, such as can be symmetricly set in sample cell for the flaky pottery well heater 15 of at least two 250 ~ 400 ohm, 200 watts, and be preferably the square sheet ceramic heater 15 of three 380 ohm, 200 watts, around the distribution triangular in shape of sample cell center, this square flaky pottery well heater is that primary heater is used for heated sample and sample cell; For described flaky pottery well heater 14, be tightly mounted on bottom sample cell by the mode of welding; The fine silver heat radiator that maximum gauge is 4 millimeters is attached with on the surface for described flaky pottery well heater 15, two, in this way, ensures that the energy efficient of well heater passes to the sample in sample cell.
A standard temperature sensor 17 is arranged on sample cell center, be specially 25 ohm of standard temperature sensor, this standard temperature sensor is the working standard grade platinum resistance temperature sensor through measurement unit certification, thermometric precision and accuracy can be ensured like this in specific heat of solid and heat metrological standard unit system, reduce the uncertainty of single unit system; At least two working temperature sensors 16 are arranged between flaky pottery well heater 15 and pool wall, and be preferably 3 100 ohm of working temperature sensors 16, this working temperature sensor accuracy is a little less than standard temperature sensor, be through measurement unit certification equally, be mainly used in the change monitoring sample temperature field in heating process in sample cell.
When described sampling receptacle 10 is for specific heat of solid and heat metrological standard unit, described working temperature sensor 16 is connected with temperature measurement system 43 by wire and vacuum high-density connector with standard temperature sensor 17, and described ceramic heater 14,15 is connected with sample heating system 42 by wire and vacuum high-density connector.The temperature of the standard temperature sensor that computing machine 45 is measured from temperature measurement system 43 retaking of a year or grade by Ethernet and the temperature of working temperature sensor, set up the models for temperature field of sample in current sample pond, and the temperature of which part is inconsistent in sample for reference pool space, then instruction is sent by Ethernet to sample heating system 42 by computing machine 45, control the well heater work of corresponding site, ensure that the uniform temperature fields of sample is consistent.
According to adiabatic tracking means 20 of the present invention as shown in Figure 3, comprise Dewar flask 21 from inside to outside successively, follow the tracks of screen 22, thermoscreen 23 and housing 24, wherein,
Described Dewar flask 21 volume can be 500 ~ 600 milliliters, such as, can be 520 milliliters; It is made up of bottle and bottle cap, and described bottle and bottle cap are made by high-temperature resistant double-layer quartz glass, and wall thickness is 2 ~ 6 millimeters, such as, can be 3 millimeters; Be vacuum at double-deck inside quartz glass and have silver coating, vacuum tightness can be 10
-5~ 10
-6pa can be such as 10
-6pa; The bottom of bottle is provided with wire hole, and can be such as 5 wire holes, for such as the temperature sensor lead of sample cell and heater conductor being worn out, wire hole be embedded with ceramic insulating tube.
In adiabatic tracking means 20, the problem that Dewar flask 21 solves said temperature gradient is set, Dewar flask belongs to one-level adiabatic apparatus, condition of high vacuum degree Dewar flask has good insulating characteristics, convection current and radiation-induced heat loss negligible, and for the conduction effect of bottleneck, then need to coordinate adiabatic screen of following the tracks of to reduce heat loss.
It is outside that described tracking screen 22 is arranged on Dewar flask 21, and be made up of red copper, volume is 3 ~ 4 liters, such as, can be 3.3 liters, and wall thickness is 3 ~ 6 millimeters, such as, can be 6 millimeters; Follow the tracks of screen 22 to form by the bottom of the bottle of closure of openings and bottle, at least two flaky pottery well heaters 221 are equipped with at bottle base fabric, such as be furnished with the flaky pottery well heater 221 of at least two 250 ~ 400 ohm, 200 watts, preferred cloth is equipped with the flaky pottery well heater 221 of three or four 250 ~ 400 ohm, 200 watts, and be equipped with temperature sensor 222 at bottle base fabric, and be provided with wire hole at the bottom of bottle, such as can arrange 5 wire holes, hole is embedded with ceramic insulating tube.
By monitoring sampling receptacle 10 temperature and tracking screen temperature, if the temperature difference of the two is greater than 0.6 degree, then start the well heater following the tracks of screen, to following the tracks of screen heating, and it is lower than sampling receptacle 10 to ensure to follow the tracks of the temperature of shielding, but the temperature difference is not more than 0.6 degree.When following the tracks of screen 22 and following the tracks of the temperature of sampling receptacle 10, although the insulation effect of Dewar flask is good, do not accomplish complete thermal insulation, if the temperature of Dewar flask both sides is consistent, then the heat leak of Dewar flask is just very little.
Described thermoscreen 23 is arranged on that to follow the tracks of screen 22 outside, and being made up of stainless steel, is sandwich construction, and at the bottom of bottle, bottle and bottle cap stud be fixed as entirety.More specifically, described thermoscreen 23 is made up of 10 layers of stainless steel cylinder, the bottle end, bottle and bottle cap stud are fixed as entirety, gap between 10 layers of stainless steel cylinder can be 4.8 millimeters, the diameter of innermost layer is 185 millimeters, and outermost diameter is 275 millimeters, and the thickness of every layer of stainless steel cylinder is 0.2 millimeter, and at the bottom of bottle, having 5 wire holes, hole is embedded with insulating ceramics pipe.Thermal convection and heat interchange is greatly reduced by the form of multi-layer cylinder.
It is outside that described housing 24 is arranged on thermoscreen 23, is made up, forms by the bottom of housing and shell of stainless steel, and housing is connected with employing vacuum seal flange at the bottom of shell, is provided with vacuum high-density connector, measuring accuracy is 0.03% pressure transducer and fill exhaust port at the bottom of shell.Housing be connected at the bottom of shell after, 1 ~ 1.3 atmospheric pressure can be born and do not reveal; Pressure transducer is used for monitoring enclosure interior and is filling the change of the pressure in exhaust process and sample heating process; Fill exhaust port and fill exhaust process for device.
Specific heat of solid and heat metrological standard unit 100 provided by the invention, comprise sampling receptacle 10, adiabatic tracking means 20, inflating and exhausting system 30 (be such as specifically as follows and automatically fill emission control 30) and Measurement and Control System 40, wherein, Measurement and Control System 40 returns examining system 41 (such as Agilent multimeter 3458A) by sample heat energy, sample heating system 42 (such as Keithley power supply 2425), temperature measurement system 43 (such as ASL bridge for measuring temperature F650), the compositions such as adiabatic tracking control system 44 (the ATCS-2000 Automatic Adiabatic controller of such as Run Tian Instrument Ltd. of Beijing Air China) and computing machine 45, Fig. 5 shows the structural representation of a concrete specific heat of solid and heat metrological standard unit 100 of the present invention.
Inflating and exhausting system 30 is for inflating to sampling receptacle 10 and adiabatic tracking means 20 and be vented, as long as may be used for carrying out inflating and being vented to sampling receptacle 10 and adiabatic tracking means 20, it is not restricted, vacuum pump evacuation such as can be adopted to be vented, the inert gas in gas cylinder can be filled with in sampling receptacle 10 and adiabatic tracking means 20 by reduction valve.In the present invention, inflating and exhausting system 30 be preferably as shown in Figure 4 automatically fill emission control 30, for inflating to sampling receptacle 10 and adiabatic tracking means 20 and be vented, this fills emission control 30 automatically by the mechanical pump of integration and molecular pump 31, retaining valve 32, gas tank 33, accurate ratio adjusting valve 34, reduction valve 36, electromagnet cut off valve 35, inert gas gas cylinder 37 and self-actuated controller 38 form, wherein, the mechanical pump of integration is connected with retaining valve 32 with molecular pump 31, retaining valve 32 is connected with gas tank 33, gas tank 33 is connected with accurate ratio adjusting valve 34, inert gas gas cylinder 37 is connected with reduction valve 36, reduction valve 36 is connected 34 with accurate ratio adjusting valve, accurate ratio adjusting valve 34 is connected with electromagnet cut off valve 35, self-actuated controller 38 controls mechanical pump and the molecular pump 31 of integration, retaining valve 32, accurate ratio adjusting valve 34, reduction valve 36, the startup of electromagnet cut off valve 35, regulate and close.
Described emission control 30 of automatically filling can be connected with the exhaust port that fills of adiabatic tracking means 20 housing 24 by electromagnet cut off valve 35, thus can inflate to sampling receptacle 10 and adiabatic tracking means 20 and be vented.Gas tank 33 does not need to control, inert gas gas cylinder 37 can manually be opened, and self-actuated controller controls mechanical pump and molecular pump 31, retaining valve 32, accurate ratio adjusting valve 34, reduction valve 36, the startup of electromagnet cut off valve 35, adjustment and the cut out that 38 control integration.Wherein, integrated mechanical pump and molecular pump 31 are used to adiabatic tracking means 20 and sampling receptacle 10 to vacuumize; Inert gas gas cylinder 37 and reduction valve 36 are used to be filled with inert gas, such as argon gas or helium, particularly preferably argon gas to adiabatic tracking means 20 and sampling receptacle 10; Inflation and exhaust process are controlled by accurate ratio adjusting valve; Electromagnet cut off valve is used for cutting off adiabatic tracking means 20 and extraneous path; The effect of gas tank keeps the pressure stability in loop.
Self-actuated controller 38 is under the instruction of the computing machine 45 of Measurement and Control System 40, with the absolute pressure in adiabatic tracking means 20 for reference, adopt fuzzy algorithm, control voltage is sent to accurate ratio adjusting valve 34, the pressure in device is slowly reduced according to the first predetermined curve, until reach the vacuum requirement of adiabatic tracking means 20, the vacustat in adiabatic tracking means 20 is controlled by pid algorithm, and a period of time is kept under this vacuum state, gas molecule is fully spread, is beneficial to residual air composition in the adiabatic tracking means 20 of emptying.Self-actuated controller 38 sends control voltage according to the second predetermined curve to accurate ratio adjusting valve 34 subsequently, under pressure transducer close-loop feedback, slow inert gas injecting (as argon gas) is required according to pressure curve, until the pressure of inert gas reaches pre-provisioning request in device, and stablizing by inert gas pressure in pid control algorithm control device, inert gas is fully spread, balances, implement device gas replenishment process.Charge, exhaust number of times can be controlled by the computing machine 45 of Measurement and Control System 40, guarantee to drain air in adiabatic tracking means 20, improve the purity inert gas in adiabatic tracking means 20, and according to the force value of inert gas in the adiabatic tracking means 20 of the accurate temperature correction in adiabatic tracking means 20, guarantee that the inert gas mass be at every turn filled with in adiabatic tracking means 20 is constant.
In specific heat of solid and heat metrological standard unit 100, the flaky pottery well heater 14 and 15 of sampling receptacle 10 returns examining system 41 with the vacuum high-density connector on housing 24 with sample heating system 42 and sample heat energy by wire and is connected; The flaky pottery well heater 221 of adiabatic tracking means 20 is connected with adiabatic tracking control system 44 with the vacuum high-density connector on housing 24 by wire; The working temperature sensor 16 of sampling receptacle 10 is connected with temperature measurement system 43 with the vacuum high-density connector on housing 24 by wire with the working temperature sensor 222 of standard temperature sensor 17 and adiabatic tracking means 20; Automatically the self-actuated controller 38 filling emission control 30 is connected by ethernet line with computing machine 45; Sample heating system 42, sample heat energy are returned examining system 41, adiabatic tracking control system 44, temperature measurement system 43 etc. and are all connected by ethernet line with computing machine 45.
Automatic inflating and exhausting system 30 is by the instruction of Ethernet receiving computer 45, automatically the process vacuumizing, be filled with inert gas (such as argon gas) of adiabatic tracking means 20 and sampling receptacle 10 is completed, and ensure pressure that original state is filled with inert gas a little less than an atmospheric pressure (because subsequent heat process, the pressure of gas can increase, in order to reduce the pressure of sealing, so the pressure being filled with inert gas in original state is a little less than an atmospheric pressure).
Adiabatic tracking control system 44 (the ATCS-2000 Automatic Adiabatic controller of such as Run Tian Instrument Ltd. of Beijing Air China) adopts great Lin sluggishness and the adaptive control algorithm based on fuzzy logic, the temperature of the tracking screen 22 in the temperature of sampling receptacle 10 and adiabatic tracking means 20 is gathered by temperature measurement system 43 (the bridge for measuring temperature F650 of such as ASL company), through Ethernet, issue adiabatic tracking control unit system 44 by computing machine 45.Adiabatic tracking control unit system 44 is by the sampling receptacle temperature of collection and follow the tracks of screen temperature relatively and carry out fuzzy reasoning, produce three parameters that PID controls, through the sluggish weighting of great Lin by the automatic regulation output power of PID, heating power is made automatically to carry out regulating, controlling along with real time temperature and design temperature deviation, realize step-less adjustment, reach the object of the fast automatic Loading Control of temperature.Guarantee that temperature following is good by Adaptive PID Control, temperature fluctuation is little, guarantees that following the tracks of screen 22 is less than 0.6K with the temperature difference of sampling receptacle 10, thus eliminates convection current and radiation-induced heat trnasfer, and reach the insulation effect of adiabatic tracking means 20.
The flaky pottery well heater 14 and 15 of sampling receptacle 10 returns examining system 41 (as Agilent multimeter 3458A) with sample heating system 42 (such as Keithley power supply 2425) and sample heat energy and is connected, computing machine 45 sends heating instructions by Ethernet to sample heating system 42, sample heat energy returns magnitude of voltage and the current value that examining system 41 reads heating circuit in real time, and sending to computing machine 45 by Ethernet, computing machine is by formula
accurately can measure and calculate the energy Q injecting sampling receptacle 10.Simultaneously, temperature measurement system 43 (the bridge for measuring temperature F650 of such as ASL company) the working temperature sensor 16 of collected specimens container 10 and the temperature value of standard temperature sensor 17, and issue computing machine 45 by Ethernet, computing machine 45 can calculate the sample temperature change Delta T after the certain energy of each input.
The above-mentioned specific heat of solid and heat metrological standard unit of employing according to the present invention measures the method for specific heat of solid and heat, the method comprises: sampling receptacle 10 and adiabatic tracking means 20 are under inert gas atmosphere, measure the thermal capacitance of empty sampling receptacle 10, then the thermal capacitance being loaded with the sampling receptacle 10 of testing sample is measured, the molar heat capacity by following formula calculation sample:
In formula: m is the quality (g) of sample,
M is the molal weight (g/mol) of sample,
C
e, c
fbe respectively sky sampling receptacle, be loaded with the mean heat capacity (J/K) of the sampling receptacle of testing sample,
C
m(T) be the mean molal heat capacity (J/molK) of sample.
Specifically describe the method adopting specific heat of solid and heat metrological standard unit of the present invention to measure specific heat of solid and heat below.
1. measure the basic functional principle of specific heat of solid and heat:
Based on Absolute Measurement principle, the adiabatic calorimetry being interrupted heating is adopted to carry out.First the equilibrium temperature of working sample container, a certain amount of electric energy is inputted to sampling receptacle, the size measuring this electric energy and the temperature of sampling receptacle caused raise, and reach the equilibrium temperature of working sample container again after balance until sampling receptacle temperature, repeat this operation until the ceiling temperature of experiment.The thermal capacitance of sampling receptacle is gone out by following formulae discovery:
In formula: V (t), I (t) are the terminal voltage (V) on well heater and heating current (A),
T is heating time period (sec),
Δ T is experiment temperature rise (K).
In the temperature range measured, measure empty sampling receptacle thermal capacitance (also known as space amount) respectively and be loaded with sampling receptacle (also known as the full container) thermal capacitance of testing sample, can by the molar heat capacity of following formula calculation sample:
In formula: m is the quality (g) of sample,
M is the molal weight (g/mol) of sample,
C
e, c
fbe respectively the mean heat capacity (J/K) of space amount, full container,
C
m(T) be the mean molal heat capacity (J/molK) of sample.
Under full container state, in sampling receptacle, amount of inert gas is than few under space amount state, produces inert gas thermal capacitance difference thus and can adopt following formula correction:
In formula: ρ
afor the density (kg/m of inert gas under space amount original state
3);
V
mfor adding the volume (m of sample under full container state
3);
M
afor the molal weight (g/mol) of inert gas under space amount original state;
C
pa(T) be the specific heat capacity of inert gas at T temperature (J/ (molK)).
According to formula above, can according to the temperature variation of empty equivalent measurement process, amendment inert gas thermal capacitance is poor.
Under experimental temperature, sample thermal capacitance experiment value is after inert gas thermal capacitance difference is revised, and adopts least square fitting to go out following polynomial expression:
In formula: C
s(T) be the sample molar heat capacity under T temperature spot;
A is the coefficient of polynomial fitting;
T is sample temperature.
The easypro level values of sample molar heat capacity can be calculated thus.
2. measuring method:
1) Preparatory work of experiment work:
Laboratory temperature remains on 20 ± 2 DEG C at experimental session.The all measuring equipments opened in specific heat of solid and heat device carry out preheating 1 ~ 2h.The Measurement and Control System of starter gear, makes it enter duty.
2) adiabatic tracking means sealing and be filled with inert gas:
After the housing 24 of adiabatic tracking means 20 is sealed, start and automatically fill emission control 30, when system vacuum reaches 1.33Pa, be filled with high purity inert gas (such as argon gas, purity is 99.99%), to a little more than 1 atmospheric pressure, then close gas charging system, start degassing function and vacuumize.Repeat above-mentioned bleeding and charge operation 3 times, finally keep the pressure of system to be 80KPa, and the force value of adiabatic tracking means inside is issued computing machine by Ethernet.
3) measurement of space amount:
Regulate sampling receptacle 10 temperature to starting experimental temperature.The speed collected specimens container 10 Plays temperature sensor of temperature measurement system according to every 10 seconds points and the temperature of working temperature sensor, through the analysis and calculation in temperature field, obtain the medial temperature of sampling receptacle at that time, then, every 20 some accounting temperature rate of change.When rate of temperature change is less than 5 × 10
-4during K/min, system reaches balance.After sampling receptacle balance period terminates, computing machine sets Implantation Energy value by Ethernet to sample heating system, and send heating instructions, export constant heating current, the adjustment rate of heat addition is 5K/min, and meanwhile, sample heat energy returns terminal voltage and the heating current of examining system Real-Time Monitoring well heater, calculate the energy size injected, temperature measurement system is with the temperature value of the continuous record standard temperature sensor of the speed of every 10 seconds points and working temperature sensor.Through the analysis and calculation in temperature field, obtain the medial temperature of sampling receptacle at that time, then, every 20 some accounting temperature rate of change.When sample heat energy return examining system detect that Implantation Energy reaches setting value time, close the output of heating current, sample heat energy is returned examining system and the data such as voltage, electric current and time is issued computing machine by Ethernet.Sampling receptacle enters the data acquisition in latter stage in this stage.Temperature measurement system continues the temperature value gathering standard temperature sensor and working temperature sensor, through the analysis and calculation in temperature field, obtains the medial temperature of sampling receptacle at that time, then, and every 20 some accounting temperature rate of change.When temperature variability is less than 5 × 10
-4during K/min, system reaches balance, and now temperature value is temperature in latter stage.The average temperature value, rate of temperature change data etc. that the standard temperature sensor of overall process, working temperature sensor, temperature field analysis calculate is issued computing machine by Ethernet by temperature measurement system.Latter stage, temperature data was also the initial stage temperature data of next heating cycle.This process is until sampling receptacle temperature is increased to the upper limit of device experimental temperature repeatedly, and empty equivalent measurement process terminates.
4) measurement of full container state thermal capacitance:
Weigh standard substance sample α-Al
2o
3about 100 grams, join in sampling receptacle 10, measure the thermal capacity of full container according to the measuring method of space amount.
3. data processing:
1) determination of temperature rise is tested each heating cycle:
The temperature data least square fitting of each heating cycle, obtains the experiment initial temperature T through heat leak correction
iwith end temperature T
f, each period of heating, the experiment temperature rise Δ T of sampling receptacle was calculated by following formula:
ΔT＝T
f-T
i
2) calculating of electric energy is inputted:
Sample heat energy returns examining system reads well heater terminal voltage V and heating current I with the speed of 25 times per second.Each heating cycle, the calculating to the energy Q that sampling receptacle inputs adopted following formula:
Wherein V, I, t are respectively voltage, electric current and heat time.
3) α-Al
2o
3the calculating of molar heat capacity:
1., under each experimental temperature, the thermal capacitance following formula of space amount, full container calculates:
2. the space amount recorded under each experimental temperature is carried out fitting of a polynomial, calculate the space calorimetric capacitance corresponding at each temperature in full container experiment according to fitting formula.
3. the space calorimetric that under each experimental temperature, the thermal capacitance of full container deducts under relevant temperature is held, and considers amount of substance, obtains α-Al under each experimental temperature
2o
3mean molal heat capacity.After carrying out every correction and fitting of a polynomial, under can bulk temperature being calculated, with 5K or 10K temperature for interval, α-Al
2o
3true molar heat capacity value.
4) uncertainty of measurement:
With America NI ST SRM720 standard substance α-Al
2o
3measure under 300 to 550K experimental temperature, obtain result as follows:
| T(K) | C p(J·mol -1·K -1) | T(K) | C p(J·mol -1·K -1) |
| 306.60 | 80.84 | 444.04 | 101.01 |
| 326.82 | 84.89 | 455.42 | 102.31 |
| 336.58 | 86.65 | 465.77 | 103.19 |
| 346.26 | 88.29 | 474.81 | 104.05 |
| 357.62 | 89.96 | 483.27 | 104.73 |
| 365.32 | 91.33 | 491.96 | 105.45 |
| 374.71 | 92.72 | 500.63 | 106.13 |
| 384.03 | 94.02 | 509.26 | 106.82 |
| 393.26 | 95.25 | 522.78 | 107.78 |
| 402.46 | 96.43 | 533.04 | 108.51 |
| 407.87 | 97.03 | 542.43 | 109.23 |
| 417.65 | 98.24 | 550.03 | 109.64 |
| 430.63 | 99.69 |
Finally evaluate the uncertainty of specific heat of solid and heat measurement result, consider the category-A uncertainty from working sample specific heat capacity measurement result repeatability, and from the category-B uncertainty outside measurement result repeatability.With standard substance α-Al
2o
3for example, its relative expanded uncertainty is about (0.1%-0.4%) (k=2).
Claims (10)
1. for the adiabatic tracking means of specific heat of solid and heat metrological standard unit, it is characterized in that, described adiabatic tracking means comprises Dewar flask (21) from inside to outside successively, follows the tracks of screen (22), thermoscreen (23) and housing (24).
2. the adiabatic tracking means for specific heat of solid and heat metrological standard unit according to claim 1, it is characterized in that, described Dewar flask (21) is made up of bottle and bottle cap, described bottle and bottle cap are made by high-temperature resistant double-layer quartz glass, be vacuum at double-deck inside quartz glass and have silver coating, vacuum tightness is 10
-5~ 10
-6pa, the bottom of bottle is provided with wire hole, and hole is embedded with ceramic insulating tube.
3. the adiabatic tracking means for specific heat of solid and heat metrological standard unit according to claim 1, it is characterized in that, it is outside that described tracking screen (22) is arranged on Dewar flask (21), be made up of red copper, and form by the bottom of the bottle of closure of openings and bottle, be equipped with at least two flaky pottery well heaters (221) at bottle base fabric, and be furnished with working temperature sensor (222), and being provided with wire hole at the bottom of bottle, hole is embedded with ceramic insulating tube.
4. the adiabatic tracking means for specific heat of solid and heat metrological standard unit according to claim 3, is characterized in that, described flaky pottery well heater is the flaky pottery well heater of 250 ~ 400 ohm, 200 watts.
5. the adiabatic tracking means for specific heat of solid and heat metrological standard unit according to claim 1, it is characterized in that, described thermoscreen (23) is arranged on follows the tracks of screen (22) outside, be made up of stainless steel, for sandwich construction, the bottle end, body and bottle cap stud are fixed as entirety, and be provided with wire hole at the bottom of bottle, hole is embedded with ceramic insulating tube.
6. the adiabatic tracking means for specific heat of solid and heat metrological standard unit according to claim 1, it is characterized in that, it is outside that described housing (24) is arranged on thermoscreen (23), be made up of stainless steel, form by the bottom of housing and shell, housing is connected with employing vacuum seal flange at the bottom of shell, is provided with vacuum high-density connector, high-precision pressure sensor and fills exhaust port at the bottom of shell.
7. the adiabatic tracking means for specific heat of solid and heat metrological standard unit according to any one of claim 1 to 6, is characterized in that, described Dewar flask (21) volume is 500 ~ 600 milliliters; Described bottle and bottle cap wall thickness are 2 ~ 6 millimeters.
8. the adiabatic tracking means for specific heat of solid and heat metrological standard unit according to any one of claim 1 to 6, is characterized in that, described tracking screen (22) volume is 3 ~ 4 liters, and wall thickness is 3 ~ 6 millimeters; Follow the tracks of screen (22) is equipped with three or four 250 ~ 400 ohm, 200 watts flaky pottery well heater (221) at bottle base fabric.
9. the adiabatic tracking means for specific heat of solid and heat metrological standard unit according to any one of claim 1 to 6, it is characterized in that, described thermoscreen (23) is made up of 10 layers of stainless steel cylinder, gap between 10 layers of stainless steel cylinder is 4.8 millimeters, the diameter of innermost layer is 185 millimeters, outermost diameter is 275 millimeters, and the thickness of every layer of stainless steel cylinder is 0.2 millimeter.
10. the adiabatic tracking means for specific heat of solid and heat metrological standard unit according to claim 1, is characterized in that, described Dewar flask (21) volume is 500 ~ 600 milliliters; It is made up of bottle and bottle cap, and described bottle and bottle cap are made by high-temperature resistant double-layer quartz glass, and wall thickness is 2 ~ 6 millimeters; Be vacuum at double-deck inside quartz glass and have silver coating, vacuum tightness can be 10
-5~ 10
-6pa; The bottom of bottle is provided with wire hole, and wire hole is embedded with ceramic insulating tube;
It is outside that described tracking screen (22) is arranged on Dewar flask (21), and be made up of red copper, volume is 3 ~ 4 liters, and wall thickness is 3 ~ 6 millimeters; Follow the tracks of screen (22) to form by the bottom of the bottle of closure of openings and bottle, the flaky pottery well heater (221) of three or four 250 ~ 400 ohm, 200 watts is equipped with at bottle base fabric, and be equipped with temperature sensor (222) at bottle base fabric, and being provided with wire hole at the bottom of bottle, hole is embedded with ceramic insulating tube;
Described thermoscreen (23) is arranged on that to follow the tracks of screen (22) outside, and being made up of stainless steel, is sandwich construction, and at the bottom of bottle, body and bottle cap stud be fixed as entirety, and be provided with wire hole at the bottom of bottle, hole is embedded with ceramic insulating tube;
It is outside that described housing (24) is arranged on thermoscreen (23), be made up of stainless steel, form by the bottom of housing and shell, housing is connected with employing vacuum seal flange at the bottom of shell, is provided with vacuum high-density connector, high-precision pressure sensor and fills exhaust port at the bottom of shell.
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