CN107044998B - The method for obtaining chemical reaction kinetics equation of the determinand under microwave heating - Google Patents
The method for obtaining chemical reaction kinetics equation of the determinand under microwave heating Download PDFInfo
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Abstract
Present invention firstly provides a kind of methods of chemical reaction kinetics equation of acquisition determinand under microwave heating, after allowing multiple determinands that the chemical reactions of different durations occurs respectively in micro-wave oven, it takes out each determinand and cools down, the chemical reaction performance level after each determinand reacts different durations is tested out with DSC, it is tested to obtain multiple detection datas according to DSC, nonlinear fitting is carried out with particle swarm algorithm and obtains chemical reaction kinetics equation of the determinand under microwave heating condition.Generally speaking, the present invention provides a kind of acquisition methods of the chemical reaction kinetics equation of determinand under microwave heating pioneeringly, and specifically provides a kind of acquisition methods of the curing degree of microwave heating solidified resin based composites.
Description
Technical field
The present invention relates to obtain chemical reaction kinetics equation field, and in particular to a kind of acquisition determinand is in microwave heating
Under chemical reaction kinetics equation method.
Background technique
Kinetics be the various physics of research, chemical factor (such as temperature, pressure, concentration, the medium in reaction system,
Catalyst, flow field and thermal field distribution, residence time destribution etc.) influence to reaction rate and corresponding reaction mechanism and mathematics
The subdiscipline of the Chemical Reaction Engineering of expression formula etc..It is, in general, that Chemical Reaction Engineering worker is mainly determined by experiment,
The relationship in reactant system between each component concentration and temperature and reaction rate is determined, to meet reaction process exploitation and reaction
The needs of device design.
Parameters of the substance in the reaction kinetics equation that microwave issues biochemical reaction are often with the substance normal
It is different under the conditions of rule heating means such as electric heating, thus be convenient for instructing industrially to the design of microwave reactor and to microwave
The control chemically reacted off field, thus need to obtain the method for chemical reaction kinetics equation of the determinand under microwave heating.
Such as polymer matrix composites are widely used with its excellent performance in fields such as aerospace, automobile ships.Hot pressing
It is widely used in always in the molding manufacture of polymer matrix composites before tank shaping process.But its cure cycle is long, money
Source waste is always the insoluble problem of conventional thermocompression jug forming greatly.In recent years, microwave heating is high-efficient with its, material is heated
Uniform advantage is valued by people, but but very fresh for the research of microwave heating solidified resin based composites mechanism
See.Research Composite Microwave cure kinetics not only contribute to the deep similarities and differences for understanding microwave curing and traditional heat cure,
More theoretical foundation is provided to the numerical simulation of microwave curing composite material.It is built to carry out composite material auxiliary energy field curing uniformity
Mould simulation study lays the foundation.
Although the method that the foundation of the chemical reaction kinetics equation under normal heating conditions has had a set of maturation, such as
Resin solidification under normal heating conditions is typically directly calculated by differential scanning calorimetry (DSC) method using DSC equipment
The suction heat release value of reactant under fixed heating rate out, directly calculates reaction activity by Arrhenius equation
Find out cure kinetics equation.Because existing DSC equipment is all to be heated by way of conduct radiation to test sample,
The result tested out is also only applicable to conventional electric heating.Not yet there is the DSC equipment of microwave heating in this field.But numerous studies
The result shows that there are also significant non-causes other than temperature bring fuel factor to the chemical reaction of resin curing process for microwave radiation
The influence of fuel factor.The conventional DSC method reason single due to equipment heating method itself, it is dynamic testing and establishing resin solidification
During mechanical equation, the nonthermal effect of microwave curing reaction can not be introduced, thus calculated result is not suitable for setting
The correlative study of resin-based composite microwave curing.Therefore establish polymer matrix composites microwave curing kinetics equation at
For sciences problems urgently to be resolved in research Composite Microwave curing proceeding.
Microwave curing in view of polymer matrix composites is only one kind in the chemical reaction under microwave heating, thus this
A kind of method that field needs to find chemical reaction kinetics equation of the acquisition determinand under microwave heating.
Summary of the invention
Therefore, the side of the chemical reaction kinetics equation present invention firstly provides a kind of acquisition determinand under microwave heating
Method, after allowing multiple determinands that the chemical reactions of different durations occurs respectively in micro-wave oven, take out each to
It surveys object and cools down, the chemical reaction performance level after each determinand reacts different durations is tested out with DSC, is tested according to DSC
Multiple detection datas are obtained, nonlinear fitting is carried out with particle swarm algorithm and obtains chemistry of the determinand under microwave heating condition
Reaction kinetics equation.
In a kind of specific embodiment, determinand be arranged in the micro-wave oven in microwave heating process
Have and inhales wave substance as prestowage.
In a kind of specific embodiment, the prestowage is solid silicon carbide, and the silicon carbide is a kind of strong suction wave material
Material.
In a kind of specific embodiment, a certain determinand is carried out under microwave heating condition using temperature sensor
Temperature monitoring simultaneously records, and measures heating curve of the determinand under microwave heating condition in real time, and obtaining abscissa is time t
The T-t curve for being temperature T with ordinate；In addition, take more parts of determinands, allow it respectively will be to after different microwave reaction durations
Survey object takes out from micro-wave oven and cooling, every part of determinand after cooling use DSC to test its reacting finisheding degree respectively；DSC
Test obtains reacting finisheding degree and multiple experimental datas of t, uses grain according to the T-t curve and the multiple experimental data
Swarm optimization carries out nonlinear fitting to get chemical reaction kinetics equation of the determinand under microwave heating condition is arrived.
Specifically, first pass through particle swarm algorithm and carry out nonlinear fitting and obtain four parameters of α-t, according to four parameters and
α-t the curve that the T-t curve is fitted.
In a kind of specific embodiment, more parts of determinands are rapidly cooled to temperature T1, and T1 after microwave reaction
For the arbitrary value between the temperature that known determinand will not chemically react, such as -20 DEG C~40 DEG C.Temperature T1 is DSC inspection
The initial temperature of survey, as long as rapid determinand temperature after cooling room temperature or it is following as long as substantially will not continue to chemistry occurs it is anti-
It answers (as solidified), but it will be appreciated by those skilled in the art that, it will with faster speed to the determinand after solidifying to a certain degree
It cools down and is sent in DSC equipment at faster speed and is detected, then is conducive to the detection for improving heretofore described method
Precision.
In a kind of specific embodiment, the temperature sensor is optical fiber or the microwave thermoelectricity with metal screen layer
It is even.
In a kind of specific embodiment, between multiple determinands the difference of microwave reaction duration two-by-two between uniform one
It causes.
In a kind of specific embodiment, the determinand is polymer matrix composites, detects to obtain using this method
The chemical reaction kinetics equation of its microwave curing.As known to those skilled in the art, polymer matrix composites are with organic poly-
The fibre reinforced materials that object is matrix is closed, usually using fibre reinforcements such as glass fibre, carbon fiber or aramid fibers.Resin base is multiple
Condensation material is widely used in aviation, automobile, marine industry.
In a kind of specific embodiment, go out complete uncured polymer matrix composites using DSC sweep test
Total thermal discharge Hu, and the solidification waste heat H of multiple determinands is tested out using DSC respectivelyrAfterwards, according to formulaIt obtains
The curing degree α of the determinand, then using time t as abscissa, the i.e. described reaction of α-t curve obtained using curing degree α as ordinate
The experimental data curve of performance level and t.
The present invention also provides a kind of acquisition methods of the curing degree of microwave heating solidified resin based composites, including should
Polymer matrix composites are heating and curing in micro-wave oven to be taken out after a certain period of time and is cooled to rapidly, then by resin after cooling
Based composites measure its curing degree α using DSC equipment；It is preferred that in microwave during the polymer matrix composites microwave curing
A certain amount of suction wave substance is placed in furnace as prestowage.
The present invention can accordingly bring it is following the utility model has the advantages that
1, in the present invention, determinand is being got after the chemical reaction kinetics equation under microwave heating, it can meter
It calculates under any Elevated Temperature Conditions, the chemical reaction course of any time point, is detected without reacting one by one, this is conducive to refer to
Lead the control industrially to chemically reacting in microwave field.
2, it is combined in the present invention using common micro-wave oven and DSC equipment and dexterously measures polymer matrix composites prepreg
The curing degree of sample microwave curing, chemical reaction kinetics equation under microwave can be acquired by reusing particle swarm algorithm.
3, it is preferable to use silicon carbide to be used as with being loaded in during determinand microwave heating chemically reacts in the present invention
Absorb microwave.Chemical reaction course under the microwave of determinand can be made to be mitigated.
5, the measured result that the method for the curing degree of the cured polymer matrix composites of microwave heating is obtained in the present invention is non-
Often stablize, such as (determinand situation, microwave power, distribution situation of prestowage etc.) repeated detection microwave is solid under identical condition
Two pieces of polymer matrix composites for changing the same time detect both resulting curing degree α data using DSC equipment and keep height one
Cause property.Illustrate that the reliability of the method for the invention is high.
Generally speaking, the present invention provides a kind of Chemical Kinetics side of determinand under microwave heating pioneeringly
The acquisition methods of journey, and specifically provide a kind of acquisition methods of the curing degree of microwave heating solidified resin based composites.
Detailed description of the invention
Fig. 1 includes that Fig. 1 (a) and Fig. 1 (b), wherein Fig. 1 (a) and Fig. 1 (b) are respectively polymer matrix composites microwave curing
The schematic diagram of T-t curve and α-t curve in the process.
Fig. 2 is the measured drawing of T-t curve and α-t curve during polymer matrix composites microwave curing.
Fig. 3 (a) is the measured result and fitting result comparison diagram of T-t curve, and Fig. 3 (b) is the measured result of α-t curve
With fitting result comparison diagram.
Specific embodiment
By taking the solidification of epoxy resin-base composite material (specifically used epoxy resin carbon fiber composite material) as an example, it is known that its
The citation form of chemical reaction kinetics equation is based on only as the self catalyzed curing model of model, citation form are as follows:
The cured chemical reaction kinetics equation of epoxy resin-base composite material and routine in the present invention, under microwave heating
The chemical reaction kinetics equation of same form is used under heating condition.Inventors have found that the equation be one about time t,
The close coupling differential equation of curing degree α and temperature T.And T itself is the function of t, therefore to obtain A, E, m, n tetra- of the equation
A parameter is it is only necessary to know that the variation relation of α-t and T-t can carry out nonlinear fitting by particle swarm algorithm and obtain, in turn
Solve its microwave curing kinetics equation.
Specifically, the paving of carbon fiber enhancement resin base composite material prepreg is put at the laminate of 25 × 25 × 1.2mm
Enter and carry out elevated cure in micro-wave oven, be also placed in micro-wave oven using solid silicon carbide as prestowage, solidification process uses 4 surveys
Warm optical fiber carries out temperature monitoring and records, and the T-t heating curve of laminate is measured in real time, as shown in Fig. 1 (a).In addition, using more
The different above-mentioned laminate of piece carries out multiplicating experiment, takes out respectively in time t=2min, 4min, 6min, 8min ...
Laminate is rapidly cooled to 0 DEG C, then carries out DSC sweep test and goes out the solidification waste heat H of every piece of laminate in this stater, separately
Also go out the uncured total thermal discharge H of prepreg completely with DSC sweep test outsideu, according to formulaIt can be concluded that this
The curing degree α of moment sample, thus can accordingly obtain the α-t curve as shown in Fig. 1 (b).
Fig. 2 is the measured drawing of T-t curve and α-t curve during polymer matrix composites microwave curing, wherein abscissa
For t, left ordinate scale T, right ordinate scale is curing degree α.
According to the empirical curve for the α-t that the T-t curve and DSC sweep test obtain, (specifically made using particle swarm algorithm
With MATlab software) matched curve that nonlinear fitting obtains α-t is carried out, wherein T-t matched curve and reality shown in Fig. 3 (a)
It is almost consistent to survey result, fit equation are as follows: T=-43.53e-2.22t-172.19e-0.29t+ 240.72, Fig. 3 (b) is α-t curve
Measured result and fitting result comparison diagram.Matched curve α-t represents following chemical reaction kinetics equation:
Experimental result discovery, the cured chemical reaction kinetics equation of epoxy resin-base composite material under microwave heating with
When using the chemical reaction kinetics equation of same form under normal heating conditions, tetra- parameter differences of A, E, m, n of the two are aobvious
It writes.It is not only to have fuel factor under microwave heating condition that this, which is also further demonstrated, is also produced to the chemical reaction of determinand
Nonthermal effect.
In addition, it should be noted that, solidifying determinand after a certain period of time using the muti-piece that DSC equipment detects in the present invention
It is mostly all uncured complete before the detection of DSC equipment, and its curing degree reaches 100% after the detection of DSC equipment.
In addition, the experimental result and fitting result of T-t involved in the present invention, and it is related to the experimental result and fitting of α-t
As a result, but the fitting result of T-t can be carried out obtaining after data processing in origin according to its experimental result, do not need
The nonlinear fitting of particle swarm algorithm is carried out in matlab.And the fitting result of α-t needs the experimental result and T-t according to α-t
Fitting result in matlab using particle swarm algorithm carry out nonlinear fitting and obtain.
In above-mentioned test by taking the cured chemical reaction kinetics equation of epoxy resin-base composite material as an example to the present invention into
Gone elaboration, if but happens is that when other chemical reactions in micro-wave oven, the model and parameter of kinetics equation accordingly with
And change.Method in the present invention can be applied to the chemical reaction kinetics equation of the various different materials under microwave heating
Solution, can disposably acquire the numerical value of each parameter in its kinetics equation.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (6)
1. a kind of method of chemical reaction kinetics equation of acquisition determinand under microwave heating, which is characterized in that the side
Method includes: the temperature monitoring and record carried out to a certain determinand using temperature sensor under microwave heating condition, is measured in real time
It is bent to obtain the T-t that abscissa is time t and ordinate is temperature T for heating curve of the determinand under microwave heating condition
Line；In addition, take more parts of determinands, it is allowed respectively to take out from micro-wave oven determinand after different microwave reaction durations and cold
But, every part of determinand after cooling uses DSC to test its reacting finisheding degree respectively；DSC tests to obtain reacting finisheding degree and t
Multiple experimental datas, reacting finisheding degree and the experimental data curve of t are established according to multiple experimental datas, according to the T-t
The experimental data curve of curve and the reacting finisheding degree and t using particle swarm algorithm carry out nonlinear fitting to get to
Survey chemical reaction kinetics equation of the object under microwave heating condition；
Go out total thermal discharge H of uncured polymer matrix composites completely using DSC sweep testu, and surveyed respectively using DSC
Try out the solidification waste heat H of multiple determinandsrAfterwards, according to formulaObtain the curing degree α of the determinand, then with time t
For abscissa, using the experimental data curve of curing degree α α-t the curve i.e. described reacting finisheding degree and t obtained as ordinate；
Use when fitting is Kamal kinetic model:。
2. method according to claim 1, which is characterized in that carried out in microwave heating process to determinand, in the microwave
It is provided in furnace and inhales wave substance as prestowage.
3. method according to claim 2, which is characterized in that the prestowage is solid silicon carbide.
4. method according to claim 1, which is characterized in that more parts of determinands are rapidly cooled to temperature after microwave reaction
T1, and T1 is the temperature that known determinand will not chemically react.
5. method according to claim 1, which is characterized in that the temperature sensor is for optical fiber or with the micro- of metal screen layer
Wave thermocouple.
6. method according to claim 1, which is characterized in that between multiple determinands the difference of microwave reaction duration two-by-two between
Uniformity.
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| CN102661930A (en) * | 2012-04-27 | 2012-09-12 | 沈阳航空航天大学 | Method used for rapidly detecting curing degrees of thermosetting materials |
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| CN102661930A (en) * | 2012-04-27 | 2012-09-12 | 沈阳航空航天大学 | Method used for rapidly detecting curing degrees of thermosetting materials |
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