CN106706700A - Online monitoring system and method for phase change-resistance relation of conductive polymer composite material - Google Patents
Online monitoring system and method for phase change-resistance relation of conductive polymer composite material Download PDFInfo
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- CN106706700A CN106706700A CN201610991926.0A CN201610991926A CN106706700A CN 106706700 A CN106706700 A CN 106706700A CN 201610991926 A CN201610991926 A CN 201610991926A CN 106706700 A CN106706700 A CN 106706700A
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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
- G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
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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
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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
- G01N25/04—Investigating or analyzing materials by the use of thermal means by investigating changes of state or changes of phase; by investigating sintering of melting point; of freezing point; of softening point
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
Abstract
The invention discloses an online monitoring system and method for a phase change-resistance relation of a conductive polymer composite material. The online monitoring system comprises a DSC (heat flow type differential scanning calorimeter) system, a sample, a high temperature-resistant thin lead, a picoammeter, a direct-current power supply, an RS-232 interface cable, a computer and a multi-value resistor; the DSC system comprises a DSC heating furnace and an alumina crucible. The online monitoring system and method disclosed by the invention have the benefits that through DSC test, a heat flow-time relation curve of a phase change behavior of the reaction sample can be obtained; meanwhile, the current change in the sample is monitored in real time under constant voltage through the picoammeter, and a sample volume resistance-time relation is obtained by calculation; the online monitoring system and method can be widely suitable for metallic and non-metallic filler-filled thermoplastic/thermosetting conductive polymer composite materials.
Description
Technical field
The present invention relates to conductive polymer composite, a kind of conductive polymer composite phase transformation-electricity is specifically related to
Resistance relation on-line monitoring system and method.
Background technology
Conductive polymer composite refers to that conductive filler is added in polymeric matrix, is prepared by various methods out
Conductive composite.Such composite has heterogeneous structure, wherein with polymeric matrix as continuous phase, conductive filler be
Dispersed phase.Due to its have the advantages that easy to process, low cost, electrical property and mechanical property can in interior regulation in a big way, because
And sensor, flexible device, ultracapacitor are widely used to, microwave absorption, energy-storage battery, electromagnetic shielding and electrochemistry etc.
Field.
The resistivity size of conductive polymer composite is generally influenceed by material temperature, when temperature changes, material
Phase and internal structure are significantly changed.For example, when thermoplastic conductive macromolecular material is heated thawing, material is by rubber
State is changed into viscous state, or direct is viscous state by crystalline transformation, and macromolecular chain motion is remarkably reinforced, and matrix viscosity is significantly
Degree is reduced, and the conductive filler (such as CNT, graphene microchip, metal particle etc.) being scattered in macromolecule matrix contacts with each other
Probability significantly improve, perfect conductive network is easily formed each other, promote resistivity of material to reduce.However, working as material
Temperature reduction, macromolecular chain is frozen or crystallizes, and thus will produce more complicated influence to material electrical property：One side
Face, the conductive path between conductive filler may be blocked by polymer crystal, thus resistivity of material raising；On the other hand, by
Shunk in matrix material, it is also possible to more conductive paths are formed between conductive filler so that resistivity of material reduction.Always
It, conductive polymer composite electrical property will be difficult to the complicated change predicted, its variation tendency and journey in phase transition process
Degree depends on matrix transformation behavior and conductive filler species.The problem for conductive polymer composite processing and forming and
The exploitation of high-performance conductive polymer composite has material impact.
Deeply to probe into the relation of conductive polymer composite transformation behavior and material electrical property, domestic and international expert is to phase
Pass field has carried out some researchs, and obtains certain achievement, such as Application No. 98126142.6《Testing conductive material structure
Electrical testing method》, it is proposed that a kind of various phases for material, on-line testing conducting material structure is surveyed with the electricity of performance
Method for testing, but this method do not illustrate to experimental provision, do not specify phase transformation and conductivity test method and as a result, and
It is not directed to the method for testing of thermosets；The paper of Tang Wen et al.《Reversible transition and conduction based on the compound containing pyrazoles
Property Quality Research》, carry out proton conductive test using pyrazoles and the hexafluorophosphoric acid compound that obtains of synthesis and understand its phase transition process
The change of middle electrical conductivity, but this method fail simultaneously to phase transition process and electrical property change measure, work and be only used for table
Transformation temperature conductance change nearby is levied, analysis is not made to overall phase transition process and electrical property variation relation.Guan Rui is in degree
Paper《The research of the electrical properties of ZnSe and ZnTe and its reversible transition under high pressure》In, the phase transformation to ZnSe under high pressure and ZnTe
Relation and conductance between is analyzed, but its be mainly applying pressure change testing conductive rate change, and just for
Single substance, it is impossible to meet the phase transformation of many kinds of substance and the demand of synchronism detection and real-time accurate Characterization both conductance, thus
Need one kind can in phase transition process accurately and reliably real-time monitoring conductive polymer composite electrical property change test system
System and method.
The content of the invention
Regarding to the issue above, in order to overcome existing technical deficiency, the invention provides a kind of conducting polymer composite wood
Material phase transformation-electrical property relation on-line monitoring system, by DSC and the Simultaneous Monitoring of pico-ampere table, in accurate sign phase transition process
Conductive polymer composite electrical property situation of change.
A kind of conductive polymer composite phase transformation-sensitivity on-line monitoring system, including DSC systems, sample, resistance to height
Warm thin wire, pico-ampere table, dc source, RS-232 interface cable, computer, many-valued resistor；The DSC systems include DSC
Heating furnace, alumina crucible；
Characterized in that, the DSC heating furnaces middle part is provided with heat-conducting plate, heat-conducting plate is provided with point for measuring temperature, by data wire
Hole through below DSC heating furnaces, is connected to computer, the sample crucible and the temperature of reference crucible that will be detected in computer
Difference is converted into differential heat flow by heat flow equation；In the DSC heating furnaces, alumina crucible side is additionally provided with reference crucible, reference
Air inside crucible is used as with reference to sample；
Electrode is processed at conductive polymer composite sample two ends, and connects high temperature resistant thin wire, is subsequently placed in oxygen
In change aluminium crucible；Alumina crucible top is provided with cap bore, the cap bore of two oxidized aluminium crucibles of high temperature resistant thin wire and DSC heating
The cap bore of stove is passed through, and is connected respectively on pico-ampere table and dc source；Structure is connected by electric wire between pico-ampere table and dc source
Into loop；Pico-ampere table connects computer by RS-232 interface cable；Dc source gives sample two end electrodes on-load voltage, pico-ampere
Electric current in table monitoring circuit, and computer is sent the data to by RS-232 interface cable, data are installed on computer
Logging software, the temperature data and current data transmitted to record heating furnace is recorded and analyzed；
DSC heating furnaces are used for oxidizing aluminium crucible and internal sample heating or lower the temperature, and DSC system monitorings sample becomes in temperature
The changes of heat flux that phase and internal structure change during change cause, while comparing with reference to sample, obtains sample and becomes in temperature
The relation figure line of hot-fluid difference-temperature in change；
The system monitors thermoplastic composite on-line in the phase such as Glass Transition and crystallization, mistake cold crystallization, fusing
During change, the real-time relationship of its internal structure-electric property-temperature three is additionally operable to monitor same with thermosetting compound material on-line
Prepolymer heat up when, occur curing reaction during above-mentioned three situation of change；In experimentation, thermosetting polymer
Prepolymer is solid-state or liquid.
Further, after the high temperature resistant thin wire is picked out from DSC heating furnaces, pressed from both sides by conductor leading and be connected to general leading
On line, winding insulating tape in junction is connected on pico-ampere table and dc source by common conductors, constitutes test loop.
Further, the sample is combined for conductive polymer composite is divided into thermal plastic high polymer by base material species
Material and thermosetting polymer composite；Composite material of thermoplastic macromolecule test specimens are shaped as uiform section rectangle, thermosetting
Polymer composite test specimens are powder or liquid, for being filled into DSC test special copples；The conducting polymer is combined
Material sample can be composited by various polymer base materials and metal, nonmetallic various and different shape filler.
Further, the high temperature resistant thin wire center material is silver core, appearance covering polytetrafluorethylecoatings coatings, overall diameter
About 0.25mm.
Further, one or more are connected with the test loop that described sample, pico-ampere table are connected with dc source
Resistor as circuit compensation resistance, can appropriate extended volume resistivity measurement range.
The present invention has been also provided to the user of conductive polymer composite phase transformation-electrical property relation on-line monitoring system
Method, in turn includes the following steps：
S1) make the sample of conductive polymer composite and determine its quality；Composite material of thermoplastic macromolecule is tested
Specimen shape is uiform section rectangle, 3~5mm, 2~4mm wide, 1~2mm of thickness long；Thermosetting polymer composite material test sample
It is powder or liquid, for being filled into DSC test special copples；
S2 sample) is connected with high temperature resistant thin wire, belt electrode sample is prepared.For different substrate materials sample, can be in high temperature resistant
The contact point of thin wire and rectangular specimen two ends fixed position is uniformly coated with conductive paste, or in alumina crucible interior sidewall surface with leading
Electric cream fixes electrode and high temperature resistant thin wire, places into sample, is made belt electrode sample；
S2.1) if sample is solid thermoplastics material, i.e. solid sample, high temperature resistant thin wire is wound into rectangular specimen two
End, two high temperature resistant thin wire spacing about 2.2mm；High temperature resistant thin wire is uniformly coated with conductive paste, sample with sample contacts position
Two ends conductive paste spacing about 2mm, normal temperature cure or is made electroded sample after being heating and curing；
S2.2) if sample is thermoset prepolymer liquid, i.e. liquor sample, two high temperature resistants carefully can be led with conductive paste first
Line is bonded at the relevant position of special aluminium oxide crucible internal walls offside, then liquor sample injection crucible is made into belt electrode sample, notes
Meaning need to control liquid quality to cover electrode；
S2.3) if sample is thermoset prepolymer solid powder, i.e. powder sample, it is used in the similar side of liquor sample
Method, two high temperature resistant thin wires is first bonded at the relevant position of special aluminium oxide crucible internal walls offside with conductive paste, then will determine
The powder sample of quality adds crucible, still needs to cover electrode, and being finally compacted powder makes its densification that contacted with each other in crucible.
S3) sample level is put into the special aluminium oxide crucible of DSC system supports, after covering crucible cover, by alumina crucible
Specified location in DSC heating furnaces is put into, such as on heat-conducting plate, reference crucible is put in correspondence position, and cover heating furnace lid；
S4) thin wire is passed through from crucible cap bore and heating furnace cap bore and draws DSC systems, and pico-ampere table and direct current are connected on respectively
On power supply respective wire cable guide, and it is fastened with insulating tape；
S5) according to material property, corresponding DSC test parameters are set and start test；Can be obtained after the completion of test sample with
With reference to heat flow poor (Δ H)-temperature (T)-time (t) triadic relation's curve of sample；
S6) in DSC test process, dc source to sample two ends on-load voltage (U), when pico-ampere table real-time monitoring and record
Circuital current (IA) with the relation data of time；After the completion of the monitoring of pico-ampere table, related data is sent out by RS-232 interface cable
Computer is sent to, and is recorded by related data logging software；
S7) according to voltage (U), electric current (IA) and specimen size, pass throughThe resistance (R) of sample can be calculated；
Pass throughThe specific insulation (ρ) of sample can be calculated, and then obtains the relation figure line of R-t and ρ-t；Wherein, w, h
It is the width and thickness of rectangular slat sample, l is the spacing of the conductive paste that rectangular slat sample two ends are applied；
S8 precise control testing time node) is needed in test process；Under dc source voltage supply：A, pico-ampere table are first begin to
Monitoring t1；B, DSC from initial temperature start program heat up when, record t2；When c, DSC are completed, t is recorded3And stop skin simultaneously
Peace table monitoring；
S9) Δ H-t, T-t, three kinds of relation figure lines of R-t are using t as conversion intermediary, or Δ H-t, T-t, three kinds of relations of ρ-t
Figure line can obtain Δ H-R-T or Δ H-ρ-T triadic relations, the i.e. pass of material hot-fluid-electrical property-temperature using t as conversion intermediary
System.
Further, prepared by specimen electrode described in the step S2, is divided into two kinds of situations：If 1) sample is solid thermoplastics
Material, i.e. solid sample, by high temperature resistant thin wire winding rectangular specimen two ends, two high temperature resistant thin wire spacing about 2.2mm；It is resistance to
High temperature thin wire is uniformly coated with conductive paste, sample two ends conductive paste spacing about 2mm, normal temperature cure or heating with sample contacts position
Electroded sample is made after solidification；If 2) sample be thermoset prepolymer liquid or powder, can be first resistance to by two with conductive paste
High temperature thin wire is bonded at the relevant position of special aluminium oxide crucible internal walls offside, then liquor sample or solid powder are added into crucible
Belt electrode sample is made, notes controlling liquid or powder quality to cover electrode；
Further, insulating tape described in the step S4 is flexible insulation adhesive tape or adhesive plaster (such as polytetrafluoroethylene (PTFE) rubber
Band), its object is to press from both sides contact site be fastened thin wire and conductor leading of adhesive tape, prevent extraneous vibration and contact electricity
The influence test result such as resistance.
Further, DSC described in the step S5 is TA-Q20 types, and temperature rate can be controlled in 1~50 DEG C/min, sweeps
Temperature range is retouched for -150~750 DEG C；Ammeter described in step S6 be Keithley-6485 types, testing current scope 0~
20mA；Dc source is Tectronix-pws4232 types, 0~30V of output voltage range；Data logging software is Keithley-
ExceLINX。
Beneficial effects of the present invention are as follows：
1st, the present invention provides a kind of conductive polymer composite phase transformation-sensitivity on-line monitoring system and method, profit
With DSC system precise control test specimens temperature rates；Using pico-ampere table, dc source and many-valued resistor, precise control electricity
The high precision electro flow valuve that Compressive Strength, conduction time and pico-ampere table are measured, can be calculated the reliable resistivity value of sample；
2nd, the monitoring of DSC sweep tests and pico-ampere table synchronously carry out, can real time reaction sample hot-fluid and electrical property relation, it is to avoid
Each species diversity existed during single-measurement.The present invention combines many-valued resistor as compensation resistance, suitably extends material
The measurement range of resistivity, is applicable to the conductive polymer composite of most of polymer base materials and all kinds of conductive fillers；
3rd, the system can also be used to monitoring on-line thermosets prepolymer in the curing process electrical property with temperature change
Change situation, in experimentation, thermosets prepolymer is solid-state or liquid.
Brief description of the drawings
Fig. 1 is a kind of structure chart of conductive polymer composite phase transformation-sensitivity on-line monitoring system in the present invention；
Fig. 2 is the Δ H-ρ-T relationship figure line of the high-density polyethylene composite material for monitoring conductive filler filling on-line；
Fig. 3 is thermoplasticity rectangle batten test master drawing；
Fig. 4 is thermosetting powder or liquid prepolymer assay maps.
In figure：1st, sample；101st, solid sample；102nd, liquor sample；2nd, electrode；3rd, high temperature resistant thin wire；4th, it is general to lead
Line；5th, insulating tape；6th, alumina crucible；7th, DSC systems；8th, DSC heating furnaces；9th, pico-ampere table；10th, dc source；11、RS-
232 interface cables；12nd, computer；13rd, many-valued resistor；14th, conductor leading folder.
Specific embodiment
The present invention is further described with reference to the accompanying drawings and examples.
Below in conjunction with the accompanying drawings 1, the present invention provides a kind of conductive polymer composite phase transformation-sensitivity on-line monitoring system
System, Fig. 1 is on-line detecting system structural scheme of mechanism provided in an embodiment of the present invention, including sample 1, electrode 2, high temperature resistant thin wire
3rd, common conductors 4, insulating tape 5, alumina crucible 6, DSC heating furnaces 8, pico-ampere table 9, dc source 10, RS-232 interface line
Cable 11, computer 12, many-valued resistor 13, conductor leading folder 14；Alumina crucible 6, DSC heating furnaces 8 and nitrogen injection dress
Put etc. and to constitute DSC systems 7.
The DSC systems model TA-Q20, crucible is U.S.'s TA alumina crucibles.
The conductive polymer composite of certain size is sized to sample 1 according to length (l), wide (w), (h) high, in examination
Conductive paste is smeared in the two ends specified location of sample 1 and high temperature resistant wire 3 is connected, is heating and curing after being made electrode 2, be placed in aluminum oxide earthenware
In crucible 6；The cap bore of two oxidized aluminium crucibles 6 of thin wire 3 and the cap bore of heating furnace lid 8 are passed through and draw DSC systems 7, point
Be not connected on the respective wire cable guide 14 of pico-ampere table 9 and dc source 10, insulating tape 5 wind high temperature resistant thin wire 3 with
Conductor leading presss from both sides 14 contact portions, constitutes current monitoring loop.Using two kinds of different conductors, have to use resistance to height in DSC
In the case that adiabator wire is connected, outside uses common conductors 4, can meet experiment demand, and can be cost-effective；
DSC heating furnaces 8 are heated or cooling effect to crucible 6 and internal sample 1, and DSC systems 7 are monitored sample 1 and become in temperature
During change, the changes of heat flux that its phase and internal structure change cause, while comparing with reference to sample (air), can obtain sample
The relation figure line of 1 hot-fluid difference-temperature both in temperature change；Related data is sent to computer 12 and records by DSC systems 7
And analyze.
High temperature resistant thin wire 3 and the connection of common conductors 4 sample 1, pico-ampere table 9, dc source 10 constitute loop, dc source
10 give the on-load voltage of 1 two end electrodes of sample 2, the electric current in the monitoring circuit of pico-ampere table 9, and by RS-232 interface cable 11 by number
According to computer 12 is sent to, recorded by data logging software.
The present invention also provides a kind of conductive polymer composite phase transformation-sensitivity on-line monitoring method, including as follows
Step：
1) sample 1 of conductive polymer composite is made, and determines sample mass；
If 2) high temperature resistant thin wire 3 is wound as shown in figure 3, sample 1 is solid thermoplastics material, i.e. solid style 101
The two ends of rectangular specimen 1, two spacing of high temperature resistant thin wire 3 about 2.2mm；High temperature resistant thin wire 3 is uniformly applied with the contact site of sample 1
Upper conductive paste (sample two ends conductive paste spacing about 2mm), normal temperature cure or is made the sample 1 of belt electrode 2 after being heating and curing；
If as shown in figure 4, sample 1 be thermoset prepolymer liquid, i.e. liquor sample 102, can be first with conductive paste by two
High temperature resistant thin wire 3 is bonded at the relevant position of special aluminium oxide crucible internal walls offside, is made electrode 2, then will determine the liquid of quality
Body sample 102 injects crucible and covers electrode 2, finally prepared belt electrode sample；
If sample 1 is thermoset prepolymer solid powder, i.e. powder sample, the similar method of liquor sample is used in, first
Two high temperature resistant thin wires 3 are bonded at the relevant position of special aluminium oxide crucible internal walls offside with conductive paste, electrode 2 is made, then
To determine that the powder sample of quality adds crucible, still need to cover electrode 2, being finally compacted powder makes its cause that contacted with each other in crucible
It is close.
3) level of sample 1 is put into the supporting special aluminium oxide crucibles 6 of DSC, and sample 1 contacts good with the bottom of alumina crucible 6
Good, surrounding is not contacted with the wall of alumina crucible 6,1/2 of the thickness of sample 1 no more than the cavity heights of alumina crucible 6；Cover crucible
Gai Hou, alumina crucible 6 is carefully put into the specified location of DSC heating furnaces, and typically using heat-conducting plate, the heat-conducting plate uses health
Copper coin, puts reference crucible, and cover heating furnace lid in specified location；
4) high temperature resistant thin wire is passed through from the cap bore of alumina crucible cap bore and heating furnace lid and draws DSC, is connect respectively
On pico-ampere table and dc source respective wire cable guide, it is fastened with insulating tape, prevents extraneous vibration and contact electricity
The influence test result such as resistance；
5) according to material property, corresponding DSC test technologies, including temperature rate (such as 10 DEG C/min), the upper limit are set
The parameter such as temperature and constant temperature time；DSC test after the completion of can obtain sample with reference to sample heat flow poor (Δ H)-temperature (T)-
Time (t) triadic relation's figure line；
6) in DSC test process, i.e., heating furnace normal work when, dc source gives sample two ends on-load voltage U (0-
30V), while pico-ampere table real-time monitoring and writing circuit electric current IAThe relation data of (0-20mA) and time；Pico-ampere table has been monitored
, be sent to relative recording data on computer data logging software by RS-232 interface cable by Cheng Hou；
According to voltage (U), electric current (IA) and specimen size, pass throughThe resistance (R) of sample can be calculated；Pass throughThe specific insulation (ρ) of sample can be calculated, and then obtains the relation figure line of R-t and ρ-t；
8) need precise control testing time node, i.e. DSC to start testing time and pico-ampere table in test process and start monitoring
Time must be synchronous；To have carried out following steps in avoiding equipment operating lag and behaviour's embodiment：Under dc source voltage supply, a,
Pico-ampere table is first begin to monitor the moment, is recorded as t1；B, DSC start to warm up the moment from preliminary set time, are recorded as t2；c、DSC
When being completed, t is recorded3And stop the monitoring of pico-ampere table, wherein t simultaneously2-t1Can calculate what pico-ampere table heated up in DSC start programs
Moment, t3-t2It is the interval material complete DSC testing times under the monitoring of pico-ampere table；
9) Δ H-t, T-t, three kinds of relation figure lines of R-t are using t as conversion intermediary, or Δ H-t, T-t, three kinds of relations of ρ-t
Figure line can obtain Δ H-R-T or Δ H-ρ-T triadic relations using t as conversion intermediary；Wherein, the hot difference of material can reflect
Sample phase and the internal error for making to bring, the situation of change of the structure, thus the method can be probed into deeply at a temperature of certain
Or in certain temperature range, the relation of material phase and structure for material electrical property；
In the above method, in test loop can also one or more resistors of serial or parallel connection as circuit compensation electricity
Resistance, with the measurement range of appropriate extended volume resistivity；Specifically, 1) when sample to be tested resistance is too small, pico-ampere table exceedes
The range upper limit, can first reduce DC power output voltage, if pico-ampere table still no to scale, it is contemplated that connect in the loop and treat
The close fixed value resistance of measuring resistance；2) when sample to be tested resistance is excessive, loop current is too small when pico-ampere table is accurately measured,
It is contemplated that on testing resistance resistance in parallel fixed value resistance close therewith；It is noted that the compensation resistance on series and parallel is not
Can be had big difference (within 10 times) with testing resistance resistance, and otherwise gained testing resistance deviation is larger.
In the above method, can be measured many by changing DSC test technologies (such as Range of measuring temp, temperature rate etc.)
Kind of polymer composite sample in different phase transformations (fusing, crystallization, cold crystallization etc.) and non-phase transformation (glass transition etc.) mistake
Cheng Zhong, the situation of change of electrical property.
Fig. 2 is the Δ H-ρ-T relationship of the high-density polyethylene composite material filled with present invention on-line monitoring conductive filler
Figure line.It can be found that being raised to during 110 DEG C from room temperature, the resistance of material slowly rises, and Δ H is declined slightly, because should
Temperature rise period material heat absorption volumetric expansion, conductive network is expanded therewith, and mutual contact probability reduces；After 110 DEG C, material is opened
Begin to melt, heat absorption is dramatically increased, and Δ H drops suddenly, start an obvious endothermic peak occur on DSC plot.In melting process, material
Material is internal to be undergone phase transition, and volume substantially expands, the good conductive network of front construction be destroyed, resistance is significantly increased.Work as material
Completely (after 140 DEG C), material is in viscous state for basic melting, and macromolecular chain locomitivity is remarkably reinforced, and makes the conduction around it
Filler has rebuild dynamic conductive network, thus resistance tends to reduction again.Wherein, the expansion of material internal conductive network and lead
The raising joint effect actually of electric filler locomitivity material conductivity, material is occurred the electricity of complexity in temperature-rise period
Resistive.
The above, is only presently preferred embodiments of the present invention, and any formal limitation is not made to the present invention, though
So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, any to be familiar with this professional technology people
Member, without departing from the scope of the present invention, when making a little change or modification using the technology contents of the disclosure above
It is the Equivalent embodiments of equivalent variations, as long as being the content without departing from technical solution of the present invention, according to technical spirit of the invention
Any simple modification, equivalent variations and the modification made to above example, still fall within the range of technical solution of the present invention.
Claims (9)
1. a kind of conductive polymer composite phase transformation-sensitivity on-line monitoring system, including DSC systems, sample, high temperature resistant
Thin wire, pico-ampere table, dc source, RS-232 interface cable, computer, many-valued resistor；The DSC systems add including DSC
Hot stove, alumina crucible；
Characterized in that, the DSC heating furnaces middle part is provided with heat-conducting plate, heat-conducting plate is provided with point for measuring temperature, is passed through by data wire
Hole below DSC heating furnaces, is connected to computer, and the sample crucible and the temperature difference of reference crucible that will be detected in computer are led to
It is differential heat flow that superheat flow is equations turned；In the DSC heating furnaces, alumina crucible side is additionally provided with reference crucible, reference crucible
Internal air is used as with reference to sample；
Electrode is processed at conductive polymer composite sample two ends, and connects high temperature resistant thin wire, is subsequently placed in aluminum oxide
In crucible；The cap bore of two oxidized aluminium crucibles of high temperature resistant thin wire and the cap bore of DSC heating furnaces are passed through, and are connected respectively to pico-ampere
On table and dc source；Sample, pico-ampere table and dc source connect and compose loop by wire；Dc source gives sample two ends electricity
Pole on-load voltage, the electric current in pico-ampere table monitoring circuit, and computer is sent the data to by RS-232 interface cable, calculate
Data logging software is installed, the temperature data and current data transmitted to record heating furnace are recorded and analyzed on machine；
DSC heating furnaces are used for oxidizing aluminium crucible and internal sample heating or lower the temperature, and DSC system monitorings sample is in temperature change mistake
The changes of heat flux that phase and internal structure change in journey cause, while compare with reference to sample, obtains sample in temperature change
The relation figure line of hot-fluid difference-temperature；
The system can monitor thermoplastic composite on-line in Glass Transition and crystallization, the phase transformation such as cold crystallization, fusing excessively
During, the real-time relationship of its internal structure-electric property-temperature three is additionally operable to on-line monitoring same with thermosetting compound material pre-
There is the situation of change of above-mentioned three during curing reaction when heating up in polymers；In experimentation, thermosetting polymer pre-polymerization
Thing is solid-state or liquid.
2. conductive polymer composite phase transformation-sensitivity on-line monitoring system according to claim 1, its feature exists
In, after the high temperature resistant thin wire is picked out from DSC heating furnaces, being pressed from both sides by conductor leading and be connected on common conductors, junction twines
Around insulating tape, it is connected on pico-ampere table and dc source by common conductors, constitutes test loop.
3. conductive polymer composite phase transformation-sensitivity on-line monitoring system according to claim 1, its feature exists
In the sample is composited by the metal or non-metallic fillers of various polymer base materials and different shape, and base material can be divided into
Thermal plastic high polymer and thermosetting polymer.
4. conductive polymer composite phase transformation-sensitivity on-line monitoring system according to claim 1, its feature exists
In the high temperature resistant thin wire center material is silver core, appearance covering polytetrafluorethylecoatings coatings, overall diameter about 0.25mm.
5. conductive polymer composite phase transformation-sensitivity on-line monitoring system according to claim 1, its feature exists
In being connected with one or more resistors as circuit in the test loop that described sample, pico-ampere table are connected with dc source
Compensation resistance, can appropriate extended volume resistivity measurement range.
6. a kind of conductive polymer composite phase transformation-sensitivity on-line monitoring method, in turn includes the following steps：
S1) make the sample of conductive polymer composite and determine its quality；Composite material of thermoplastic macromolecule test sample
It is shaped as uiform section rectangle, 3~5mm, 2~4mm wide, 1~2mm of thickness long；Thermosetting polymer composite material test sample is powder
End or liquid, for being filled into DSC test special copples；
S2 sample) is connected with high temperature resistant thin wire, belt electrode sample is prepared.For different substrate materials sample, can carefully be led in high temperature resistant
Line is uniformly coated with conductive paste with the contact point of rectangular specimen two ends fixed position, or in alumina crucible interior sidewall surface conductive paste
Electrode and high temperature resistant thin wire are fixed, sample is placed into, belt electrode sample is made；
S3) sample level is put into the special aluminium oxide crucible of DSC system supports, after covering alumina crucible lid, by aluminum oxide earthenware
Crucible is put into DSC heating furnaces on heat-conducting plate, reference crucible is put beside alumina crucible, and cover heating furnace lid；
S4) thin wire is passed through from crucible cap bore and heating furnace cap bore and draws DSC systems, and pico-ampere table and dc source are connected on respectively
On respective wire cable guide, and it is fastened with insulating tape；
S5) according to material property, corresponding DSC test parameters are set and start test；Sample and reference can be obtained after the completion of test
Heat flow difference-temperature-time triadic relation's curve of sample；
S6) in DSC test process, dc source is to sample two ends on-load voltage (U), pico-ampere table real-time monitoring and writing circuit electricity
Stream (IA) with the relation data of time；After the completion of the monitoring of pico-ampere table, related data is sent to by meter by RS-232 interface cable
Calculation machine, and recorded by related data logging software；
S7) according to voltage (U), electric current (IA) and specimen size, pass throughThe resistance (R) of sample can be calculated；Pass throughThe specific insulation (ρ) of sample can be calculated, and then obtains the relation figure line of R-t and ρ-t；Wherein, w, h are square
The width and thickness of shape strip sample, l are the spacing of the conductive paste that rectangular slat sample two ends are applied；
S8 precise control testing time node) is needed in test process；Under dc source voltage supply：A, pico-ampere table are first begin to monitoring
t1；B, DSC from initial temperature start program heat up when, record t2；When c, DSC are completed, t is recorded3And stop pico-ampere table simultaneously
Monitoring；
S9) Δ H-t, T-t, three kinds of relation figure lines of R-t are using t as conversion intermediary, or Δ H-t, T-t, three kinds of relation figure lines of ρ-t
Using t as conversion intermediary, Δ H-R-T or Δ H-ρ-T triadic relations, the i.e. relation of material hot-fluid-electrical property-temperature are can obtain.
7. conductive polymer composite phase transformation-sensitivity on-line monitoring method according to claim 6, its feature exists
In prepared by specimen electrode described in the step S2, including following situation：
S2.1) if sample is solid thermoplastics material, i.e. solid sample, by high temperature resistant thin wire winding rectangular specimen two ends, two
Root high temperature resistant thin wire spacing about 2.2mm；High temperature resistant thin wire is uniformly coated with conductive paste with sample contacts position, and sample two ends are led
Electric cream spacing about 2mm, normal temperature cure or is made electroded sample after being heating and curing；
S2.2) if sample is thermoset prepolymer liquid, i.e. liquor sample, two high temperature resistant thin wires can be glued with conductive paste first
In the relevant position of special aluminium oxide crucible internal walls offside, then liquor sample injection crucible is made belt electrode sample, notes needing
Control liquid quality is to cover electrode；
S2.3) if sample is thermoset prepolymer solid powder, i.e. powder sample, the similar method of liquor sample is used in, first
Two high temperature resistant thin wires are bonded at the relevant position of special aluminium oxide crucible internal walls offside with conductive paste, then quality will be determined
Powder sample adds crucible, still needs to cover electrode, and being finally compacted powder makes its densification that contacted with each other in crucible.
8. conductive polymer composite phase transformation-sensitivity on-line monitoring method according to claim 6, its feature exists
In insulating tape described in the step S4 is flexible insulation adhesive tape or adhesive plaster, carefully lead its object is to is fastened with adhesive tape
Line presss from both sides contact site with conductor leading, prevents extraneous vibration and contact resistance etc. from influenceing test result.
9. conductive polymer composite phase transformation-sensitivity on-line monitoring method according to claim 6, its feature exists
Be TA-Q20 types in, DSC described in the step S5, temperature rate can be controlled in 1~50 DEG C/min, scanning temperature range for-
150~700 DEG C；Ammeter described in step S6 is Keithley-6485 types, 0~20mA of testing current scope；Dc source is
Tectronix-pws4232 types, 0~30V of output voltage range；Data logging software is Keithley-ExceLINX.
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