CN102407595A - On-line measuring method and apparatus for degree of crystallization of polymer used for injection molding - Google Patents

On-line measuring method and apparatus for degree of crystallization of polymer used for injection molding Download PDF

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CN102407595A
CN102407595A CN2011102146979A CN201110214697A CN102407595A CN 102407595 A CN102407595 A CN 102407595A CN 2011102146979 A CN2011102146979 A CN 2011102146979A CN 201110214697 A CN201110214697 A CN 201110214697A CN 102407595 A CN102407595 A CN 102407595A
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赵朋
傅建中
贺永
陈子辰
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Zhejiang University ZJU
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Abstract

The invention discloses an on-line measuring method and apparatus for the degree of crystallization of a polymer used for injection molding. The method comprises the following steps: 1) acquiring the density of a complete crystal region of a polymer and the temperature-density curve of a complete noncrystal region of the polymer; 2) acquiring the density of a complete noncrystal region of a polymer melt in a die; 3) employing supersonic wave for real time detection of the current density of the polymer melt in the die and obtaining the real time degree of crystallization of the polymer melt according to the current density detected, the density of the complete crystal region and the density of the complete noncrystal region. The apparatus provided in the invention comprises a sensor unit, a data acquisition unit and a central processing unit, wherein, the sensor unit comprises a supersonic wave detection unit and a temperature sensor, the supersonic wave detection unit comprises a supersonic wave emitting unit and a supersonic wave receiving unit, and the temperature sensor and the supersonic wave receiving unit are respectively connected with the central processing unit through the data acquisition unit. The invention enables on-line measuring of the degree of crystallization of a polymer in the process of injection molding to be realized; the apparatus provided in the invention has the advantages of a low price and convenient usage.

Description

The polymer crystallization degree On-line Measuring Method and the device that are used for Shooting Technique
Technical field
The present invention relates to polymer injection moulding field, be specifically related to the On-line Measuring Method and the device of polymer crystallization degree in the process of injection molding.
Background technology
Injection moulding is the main means of high-performance polymer production of articles, and the engineering polymers goods more than 80% are all produced via injection molding process according to statistics.In the injection molding manufacturing technique process, form the physical and mechanical properties such as intensity, rigidity, hot property and transparency that the polymer crystallization degree that also finally is solidificated in the goods directly has influence on goods.For example when polyacrylic degree of crystallinity increases to 95% by 70%; Its hot strength can be brought up to 42MPa by 27.5MPa; When polyacrylic degree of crystallinity is respectively 70%, 95%; Its notched Izod impact strength is respectively 15.2kgcm/cm2 and 4.77kgcm/cm2, therefore polyacrylic hot strength with degree of crystallinity increase, polyacrylic impact strength then reduces with the increase of degree of crystallinity.Therefore, the height of degree of crystallinity has very big influence to the performance of polymer product, thereby in injection molding process, controls the inevitable requirement that crystallinity of polymer is the high-quality injection mo(u)lding of realization in real time.
Yet the measurement to the polymer crystallization degree up to now also rests on the on-line measurement stage under off-line measurement or the simple processing conditions.Conventional method such as differential scanning calorimetry (DSC), low angle laser light scattering (SALS) and SEM (SEM) etc.; Generally can only off-line measurement; Measurement result also can only be explained the crystal habit that moulded products is final, can't observe generation, the evolution of crystalline texture in the forming process and decide the structure process.Some scholars have proposed some on-line measurement theory and methods to simple processing environment, as employing such as Huo be with the petrographic microscope on-line tracing of shear heat platform studied the PP material in the stable state flow field, low shear rate (10 -1s -1～10s -1) effect under crystallization behavior; See Huo H; Jiang S, An L, Feng J.Influence of shear on crystallization behavior of the β phase in isotactic polypropylene with β-nucleating agent.Macromolecules; 2004,37 (7): 2478-2483.Polymer melt receives non-isothermal field, high shear field (10 in the actual injection moulding 3s -1～10 4s -1) and the comprehensive function of elongational flow field, widely different with simple condition, the result of study that simple processing environment is obtained down is very limited to the directive function of actual production technology.Shen Kaizhi etc. have developed the outfield morphology Control shaped device that the online detection polymer of laser condensed state changes; See Shen Kaizhi; Deng Cong, Li Zhongming. the outfield morphology Control shaped device that the online detection polymer of laser condensed state changes. number of patent application: CN200920080699.1.But this technical scheme is only applicable to transparent material; And most of crystal polymer thing all is translucent or opaque; Also there is apparatus expensive in this device, uses loaded down with trivial details and problem such as versatility is not strong simultaneously, and certain limitation is arranged in commercial Application, is used for laboratory research at present more.
Summary of the invention
The technical problem that the present invention will solve provides a kind of the polymer crystallization degree On-line Measuring Method and the device that are used for Shooting Technique cheap, easy to use.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is:
A kind of polymer crystallization degree On-line Measuring Method that is used for Shooting Technique, implementation step is following:
1) obtains the complete crystal region density p of polymer c, obtain the complete amorphous area temperature-density curve of polymer;
2) detect the current melt temperature T of in-site polymerization thing melt in real time a, according to
ρ a = ρ 1 - ( ρ 1 - ρ 2 ) × ( T 1 - T a ) ( T 1 - T 2 )
Calculate the complete amorphous area density p of in-site polymerization thing melt a, T wherein 1And T 2Be said complete amorphous area temperature-density curve middle distance melt temperature T aTwo nearest temperature values, ρ 1Be temperature value T 1Pairing density value, ρ 2Be temperature value T 2Pairing density value;
3) adopt ultrasonic wave to detect the current density p of in-site polymerization thing melt in real time, and according to
X c = ( 1 / ρ a ) - ( 1 / ρ ) ( 1 / ρ a ) - ( 1 / ρ c )
Obtain the real-time crystallinity X of polymer melt c
Be used for the further improvement of the polymer crystallization degree On-line Measuring Method of Shooting Technique as the present invention:
Adopting ultrasonic wave to detect the current density p of in-site polymerization thing melt in real time in the said step 3) specifically is meant:
(1), according to Z m=ρ m* v mObtain the acoustic impedance value Z of mould m, ρ wherein mDensity of material, V for mould mBe the spread speed of ultrasonic wave in mold materials;
(2), send ultrasonic signal from the mould outside to polymer melt; Obtain first ultrasonic signal that the mould polymer interface that leans on ultrasonic wave sound source one side returns, obtain second ultrasonic signal that the mould polymer interface away from ultrasonic wave sound source one side returns, and obtain from sending ultrasonic signal to the time t that receives first ultrasonic signal 1, obtain from sending ultrasonic signal to the time t that receives second ultrasonic signal 2
(3), in real time according to r=A 1/ A 0Obtain the ultrasonic reflection coefficient r of mould polymer interface, wherein A 0For sending the sound pressure level of ultrasonic signal, A 1Sound pressure level for said first ultrasonic signal;
(4), in real time according to v p=2d/ (t 2-t 1) obtain the spread speed V of ultrasonic wave in in-site polymerization thing melt p, wherein d is the die cavity thickness of ultrasonic signal transmit direction mould;
(5), real-time basis
ρ = ( 1 - r ) Z m ( 1 + r ) υ p
Obtain the current density p of in-site polymerization thing.
The ultrasonic reflection coefficient r that obtains the mould polymer interface in the said step (3) also comprises the step of first ultrasonic signal that receives being carried out Filtering Processing before; Said Filtering Processing specifically is meant at first decomposes through wavelet transformation first ultrasonic signal; Then first ultrasonic signal after decomposing is carried out reconstruct through the inverse transformation of wavelet transformation, obtain removing first ultrasonic signal of noise.
Obtain the complete crystal region density p of polymer in the said step 1) cSpecifically be meant basis
ρ c = ( Σ N i A i ) / N ~ V c
Obtain the density p of complete crystal region polymer c, V wherein cBe the volume of polymer structure cell, A iBe the relative atomic mass of i kind atom, N iFor containing the quantity of i kind atom in each polymer structure cell,
Figure BDA0000079598030000032
Be avogado constant.
The complete amorphous area temperature-density curve that obtains polymer in the said step 1) specifically is meant: polymer sample is warming up to a plurality of probe temperatures respectively and quenches and to process complete amorphous sample; Detect the density of complete amorphous sample under each probe temperature respectively, obtain the complete amorphous area temperature-density curve of polymer.
The present invention also provides a kind of polymer crystallization degree on-line measurement device that is used for Shooting Technique; Comprise sensor unit, data acquisition unit and CPU; Said sensor unit comprises ultrasonic listening unit and the temperature sensor of being located in the mould; Said ultrasonic listening unit comprises ultrasonic transmitting element and ultrasonic wave receiving element, and said temperature sensor, ultrasonic wave receiving element link to each other with CPU through data acquisition unit respectively.
Be used for the further improvement of the polymer crystallization degree on-line measurement device of Shooting Technique as the present invention:
Said CPU comprises that the ultrasonic signal that is used for input removes the signal de-noising unit of making an uproar and handling; Said signal de-noising unit comprises the ultrasonic wave decomposing module ultrasonic wave reconstructed module that inverse transformation is carried out reconstruct to ultrasonic wave with the employing wavelet transformation that adopts wavelet transformation that ultrasonic wave is decomposed, and said ultrasonic wave reconstructed module links to each other with data acquisition unit through the ultrasonic wave decomposing module.
Originally the polymer crystallization degree On-line Measuring Method that is used for Shooting Technique has following advantage:
1, the present invention obtains the complete crystal region density of polymer, complete amorphous area temperature-density curve through prediction; The temperature and the density of actual measurement polymer realize the real-time detection to degree of crystallinity; Can realize the polymer crystallization degree on-line measurement of Shooting Technique, have advantage cheap, simple in structure, easy to use.
2, the present invention realizes the Density Detection to polymer melt through ultrasonic wave; Make full use of characteristics such as hyperacoustic penetration capacity is strong, feedback speed is fast, abundant in content and easy to use; Has the advantage that detection speed is fast, detection is quick and convenient, the scope of application is wide; A kind of experiment measuring means of brand-new universality are provided for the research of polymer crystallization process; Having solved traditional polymer degree of crystallinity measuring method can only off-line measurement, or the limitation of simple processing conditions on-line measurement down, and a difficult problem such as traditional measurement method (like SALS, X ray etc.) apparatus expensive, the use that exist be loaded down with trivial details.The present invention is used for the polymer crystallization degree on-line measurement device of Shooting Technique owing to have and the above-mentioned corresponding structure of polymer crystallization degree On-line Measuring Method that is used for Shooting Technique, therefore also possesses the above-mentioned corresponding advantage of polymer crystallization degree On-line Measuring Method that is used for Shooting Technique.
Description of drawings
Fig. 1 is the implementing procedure sketch map of the embodiment of the invention.
Fig. 2 is the temperature-density curve sketch map of the complete amorphous area polymer of the embodiment of the invention.
Fig. 3 detects the implementing procedure sketch map of polymer melt density for the embodiment of the invention.
Fig. 4 is reflection and the transmission behavior sketch map of embodiment of the invention ultrasonic wave in mould cavity.
The ultrasonic signal waveform example figure that Fig. 5 receives for the embodiment of the invention.
Fig. 6 is the frame structure sketch map of the embodiment of the invention.
Fig. 7 is the detailed framework structural representation of the embodiment of the invention.
Marginal data: 1, sensor unit; 11, ultrasonic listening unit; 111, ultrasonic transmitting element; 112, ultrasonic wave receiving element; 12, temperature sensor; 2, data acquisition unit; 3, CPU; 31, signal de-noising unit; 311, ultrasonic wave decomposing module; 312, ultrasonic wave reconstructed module.
The specific embodiment
In the present embodiment, polymeric material is selected polyethylene (PE) for use, Shooting Technique parameter following:
Technological parameter Numerical value Technological parameter Numerical value
Injection temperature (℃) 220 Dwell pressure (MPa) 45
Mold temperature (℃) 40 Dwell time (s) 20
Inject time (s) 1 Cool time (s) 20
As shown in Figure 1, the implementation step of polymer crystallization degree On-line Measuring Method that present embodiment is used for Shooting Technique is following:
1) obtains the complete crystal region density p of polymer c, obtain the complete amorphous area temperature-density curve of polymer;
2) detect the current melt temperature T of in-site polymerization thing melt in real time a, according to
ρ a = ρ 1 - ( ρ 1 - ρ 2 ) × ( T 1 - T a ) ( T 1 - T 2 )
Calculate the complete amorphous area density p of in-site polymerization thing melt a, T wherein 1And T 2Be complete amorphous area temperature-density curve middle distance melt temperature T aTwo nearest temperature values, ρ 1Be temperature value T 1Pairing density value, ρ 2Be temperature value T 2Pairing density value;
3) adopt ultrasonic wave to detect the current density p of in-site polymerization thing melt in real time, and according to
X c = ( 1 / ρ a ) - ( 1 / ρ ) ( 1 / ρ a ) - ( 1 / ρ c )
Obtain the real-time crystallinity X of polymer melt c
Obtain the complete crystal region density p of polymer in the step 1) cSpecifically be meant basis
ρ c = ( Σ N i A i ) / N ~ V c
Obtain the density p of complete crystal region polymer c, V wherein cBe the volume of polymer structure cell, A iBe the relative atomic mass of i kind atom, N iFor containing the quantity of i kind atom in each polymer structure cell,
Figure BDA0000079598030000052
For avogado constant (or is claimed Avogadro constant, is worth and does
Figure BDA0000079598030000053
Individual/mole).The sub polyethylene subchain is the planar zigzag form conformation in crystal, its unit cell volume V c=9.2 * 10 -23, comprise 4 C atoms in each structure cell, 8 H atoms, therefore poly complete crystal density ρ c=(12 * 4+1 * 8)/(9.2 * 10 -23* 6.02 * 10 23)=1.01g/cm 3
The complete amorphous area temperature-density curve that obtains polymer in the step 1) specifically is meant: polymer sample is warming up to a plurality of probe temperatures respectively and quenches and to process complete amorphous sample; Detect the density of complete amorphous sample under each probe temperature respectively, the complete amorphous area temperature-density curve that obtains polymer is as shown in Figure 2.
In the present embodiment, use that same ultrasonic probe is double to be done emission and accept ultrasonic signal, utilize ultrasonic wave to incide on two kinds of different medium interfaces to take place the phenomenon of reflection and transmission, the density p of polymer in the on-line measurement process of injection molding.Detect the current melt temperature T of in-site polymerization thing melt a, adopt ultrasonic wave to detect the current density p of in-site polymerization thing melt in real time to obtain through the computer synchronous detecting.The signals collecting mode comprises: interrupt mode, half-full inquiry mode and software mode, signal acquisition periods are 1ms.
Step 2) thermocouple induction is 162.6 ℃ to this moment polymer-melt temperature value in.In that fully the amorphous area polymer temperature-162.6 ℃ of two nearest temperature values of density curve middle distance melt temperature value are T 1=160.3 ℃ and T 2=165.5 ℃, temperature is respectively at T 1And T 2The time polymer complete amorphous area density p 1=0.773g/cm 3And ρ 2=0.769g/cm 3, linear interpolation can obtain the density p of complete amorphous area polymer under this temperature a=0.773-[(0.773-0.769) * (160.3-162.6)]/(160.3-165.5)=0.771g/cm 3
As shown in Figure 3, adopt ultrasonic wave to detect the current density p of in-site polymerization thing melt in real time in the step 3) and specifically be meant:
(1), according to Z m=ρ m* v mObtain the acoustic impedance value Z of mould m, ρ wherein mDensity of material, V for mould mBe the spread speed of ultrasonic wave in mold materials.In the present embodiment, the density p of mold materials mBe 8.2g/cm 3, the speed v that ultrasonic wave is propagated in mold materials mBe 5.2 * 10 5Cm/s, the acoustic impedance value Z of mold materials m=8.2 * 52 * 10 5=42.64 * 10 5Gs/cm 2
(2), send ultrasonic signal from the mould outside to polymer melt; Obtain first ultrasonic signal that the mould polymer interface that leans on ultrasonic wave sound source one side returns, obtain second ultrasonic signal that the mould polymer interface away from ultrasonic wave sound source one side returns, and obtain from sending ultrasonic signal to the time t that receives first ultrasonic signal 1, obtain from sending ultrasonic signal to the time t that receives second ultrasonic signal 2In the present embodiment, the thickness of measured place mold cavity is 0.25cm, signal U 1, U 2Pairing time t during appearance 1=3.24 * 10 -6S, t 2=6.96 * 10 -6S.
(3), in real time according to r=A 1/ A 0Obtain the ultrasonic reflection coefficient r of mould polymer interface, wherein A 0For sending the sound pressure level of ultrasonic signal, A 1It is the sound pressure level of first ultrasonic signal; In the present embodiment, signal U 0Sound pressure level A 0Be 180mV, signal U 0Sound pressure level A 1Be 171mV, the ultrasonic reflection coefficient r=171/180=0.95 of mould/polymer interface.
(4), in real time according to v p=2d/ (t 2-t 1) obtain the spread speed V of ultrasonic wave in in-site polymerization thing melt p, wherein d is the die cavity thickness of ultrasonic signal transmit direction mould, the speed v that ultrasonic wave is propagated in polymer melt p=0.5/ (6.96 * 10 -6-3.24 * 10 -6)=1.344 * 10 5Cm/s;
(5), real-time basis
ρ = ( 1 - r ) Z m ( 1 + r ) υ p
Obtain the current density p of in-site polymerization thing.In the present embodiment, the density p of polymer=[(1-0.95) * 42.64 * 10 5]/[(1+0.95) * 1.344 * 10 5]=0.813g/cm 3
Like Fig. 4 and shown in Figure 5, when ultrasonic wave is impinged perpendicularly in the polymer melt by the mould wall, because mold materials and polymeric material acoustic characteristic is different, transmission and reflex can take place at mould/polymer interface in sound wave.In the present embodiment, raw ultrasound signals is labeled as U 0, first ultrasonic signal is labeled as U 1, second ultrasonic signal is labeled as U 2, U 0Sound pressure level be A 0, U 1Sound pressure level be A 1, according to ultrasonic signal U 0, U 1, U 2Sound pressure level and time of occurrence, the density value of polymer in the on-line measurement process of injection molding.
In the present embodiment; The ultrasonic reflection coefficient r that obtains the mould polymer interface in the step (3) also comprises the step of first ultrasonic signal that receives being carried out Filtering Processing before; Filtering Processing specifically is meant at first decomposes through wavelet transformation first ultrasonic signal; Then first ultrasonic signal after decomposing is carried out reconstruct through the inverse transformation of wavelet transformation, obtain removing first ultrasonic signal of noise.Utilize wavelet transformation and inverse transformation thereof that ultrasonic signal is carried out decomposition and reconstruction, the yardstick that can significantly portray echo-signal is reconfigured, suppress noise signal, improve signal to noise ratio, improve accuracy of detection.
In the present embodiment sometime, the complete density p of crystal region polymer c=1.01g/cm 3, the density polymer ρ=0.813g/cm of actual measurement 3, so basis
X c = ( 1 / ρ a ) - ( 1 / ρ ) ( 1 / ρ a ) - ( 1 / ρ c )
Can obtain this moment crystallinity of polymer X c=[(1/0.771)-(1/0.813)]/[(1/0.771)-(1/1.01)]=0.218.
As shown in Figure 6; The polymer crystallization degree on-line measurement device that present embodiment is used for Shooting Technique comprises sensor unit 1, data acquisition unit 2 and CPU 3; Sensor unit 1 comprises ultrasonic listening unit 11 and the temperature sensor of being located in the mould 12; Ultrasonic listening unit 11 comprises ultrasonic transmitting element 111 and ultrasonic wave receiving element 112, and temperature sensor 12, ultrasonic wave receiving element 112 link to each other with CPU 3 through data acquisition unit 2 respectively.
In the present embodiment, ultrasonic listening unit 11 adopts ultrasonic probe to realize, has ultrasonic transmitting element 111 and ultrasonic wave receiving element 112 on the ultrasonic probe simultaneously.CPU 3 comprises that the ultrasonic signal that is used for input removes the signal de-noising unit 31 of making an uproar and handling; Signal de-noising unit 31 comprises the ultrasonic wave decomposing module 311 ultrasonic wave reconstructed module 312 that inverse transformation is carried out reconstruct to ultrasonic wave with the employing wavelet transformation that adopts wavelet transformation that ultrasonic wave is decomposed, and ultrasonic wave reconstructed module 312 links to each other with data acquisition unit 2 through ultrasonic wave decomposing module 311.
As shown in Figure 7, temperature sensor 12 adopts thermocouple in the present embodiment, and thermocouple is used to detect the temperature signal of mould internal induction polymer melt.Data acquisition unit 2 adopts data collecting card to realize; Data collecting card inside comprises modules such as input amplifier, active filter, variable connector, digital-to-analogue conversion, logic control, sampling maintenance, digital-to-analogue conversion, is mainly used in the ultrasonic signal that collects, temperature signal are transferred to CPU 3 and handle through signal amplification, high speed analog-to-digital conversion.CPU 3 adopts computer realization, and ultrasonic wave decomposing module 311 adopts software to realize with ultrasonic wave reconstructed module 312.
The above is merely preferred implementation of the present invention, and protection scope of the present invention is not limited in above-mentioned embodiment, and every technical scheme that belongs to the principle of the invention all belongs to protection scope of the present invention.For a person skilled in the art, some improvement and the retouching under the prerequisite that does not break away from principle of the present invention, carried out, these improvement and retouching also should be regarded as protection scope of the present invention.

Claims (7)

1. polymer crystallization degree On-line Measuring Method that is used for Shooting Technique is characterized in that implementation step is following:
1) obtains the complete crystal region density p of polymer c, obtain the complete amorphous area temperature-density curve of polymer;
2) detect the current melt temperature T of in-site polymerization thing melt in real time a, according to
ρ a = ρ 1 - ( ρ 1 - ρ 2 ) × ( T 1 - T a ) ( T 1 - T 2 )
Calculate the complete amorphous area density p of in-site polymerization thing melt a, T wherein 1And T 2Be said complete amorphous area temperature-density curve middle distance melt temperature T aTwo nearest temperature values, ρ 1Be temperature value T 1Pairing density value, ρ 2Be temperature value T 2Pairing density value;
3) adopt ultrasonic wave to detect the current density p of in-site polymerization thing melt in real time, and according to
X c = ( 1 / ρ a ) - ( 1 / ρ ) ( 1 / ρ a ) - ( 1 / ρ c )
Obtain the real-time crystallinity X of polymer melt c
2. the polymer crystallization degree On-line Measuring Method that is used for Shooting Technique according to claim 1 is characterized in that: adopt ultrasonic wave to detect the current density p of in-site polymerization thing melt in real time in the said step 3) and specifically be meant:
(1), according to Z m=ρ m* v mObtain the acoustic impedance value Z of mould m, ρ wherein mDensity of material, V for mould mBe the spread speed of ultrasonic wave in mold materials;
(2), send ultrasonic signal from the mould outside to polymer melt; Obtain first ultrasonic signal that the mould polymer interface that leans on ultrasonic wave sound source one side returns, obtain second ultrasonic signal that the mould polymer interface away from ultrasonic wave sound source one side returns, and obtain from sending ultrasonic signal to the time t that receives first ultrasonic signal 1, obtain from sending ultrasonic signal to the time t that receives second ultrasonic signal 2
(3), in real time according to r=A 1/ A 0Obtain the ultrasonic reflection coefficient r of mould polymer interface, wherein A 0For sending the sound pressure level of ultrasonic signal, A 1Sound pressure level for said first ultrasonic signal;
(4), in real time according to v p=2d/ (t 2-t 1) obtain the spread speed V of ultrasonic wave in in-site polymerization thing melt p, wherein d is the die cavity thickness of ultrasonic signal transmit direction mould;
(5), real-time basis
ρ = ( 1 - r ) Z m ( 1 + r ) υ p
Obtain the current density p of in-site polymerization thing.
3. the polymer crystallization degree On-line Measuring Method that is used for Shooting Technique according to claim 2; It is characterized in that: the ultrasonic reflection coefficient r that obtains the mould polymer interface in the said step (3) also comprises the step of first ultrasonic signal that receives being carried out Filtering Processing before; Said Filtering Processing specifically is meant at first decomposes through wavelet transformation first ultrasonic signal; Then first ultrasonic signal after decomposing is carried out reconstruct through the inverse transformation of wavelet transformation, obtain removing first ultrasonic signal of noise.
4. according to claim 1 or the 2 or 3 described polymer crystallization degree On-line Measuring Method that are used for Shooting Technique, it is characterized in that: the complete crystal region density p of obtaining polymer in the said step 1) cSpecifically be meant basis
ρ c = ( Σ N i A i ) / N ~ V c
Obtain the density p of complete crystal region polymer c, V wherein cBe the volume of polymer structure cell, A iBe the relative atomic mass of i kind atom, N iFor containing the quantity of i kind atom in each polymer structure cell,
Figure FDA0000079598020000022
Be avogado constant.
5. according to claim 1 or the 2 or 3 described polymer crystallization degree On-line Measuring Method that are used for Shooting Technique; It is characterized in that the complete amorphous area temperature-density curve that obtains polymer in the said step 1) specifically is meant: polymer sample is warming up to a plurality of probe temperatures respectively and quenches and to process complete amorphous sample; Detect the density of complete amorphous sample under each probe temperature respectively, obtain the complete amorphous area temperature-density curve of polymer.
6. polymer crystallization degree on-line measurement device that is used for Shooting Technique; It is characterized in that: comprise sensor unit (1), data acquisition unit (2) and CPU (3); Said sensor unit (1) comprises ultrasonic listening unit (11) and is located at the temperature sensor (12) in the mould; Said ultrasonic listening unit (11) comprises ultrasonic transmitting element (111) and ultrasonic wave receiving element (112), and said temperature sensor (12), ultrasonic wave receiving element (112) link to each other with CPU (3) through data acquisition unit (2) respectively.
7. the polymer crystallization degree on-line measurement device that is used for Shooting Technique according to claim 6; It is characterized in that: said CPU (3) comprises that the ultrasonic signal that is used for input removes the signal de-noising unit (31) of making an uproar and handling; Said signal de-noising unit (31) comprises and adopts wavelet transformation to ultrasonic wave ultrasonic wave decomposing module (311) of decomposing and the ultrasonic wave reconstructed module (312) that adopts the wavelet transformation inverse transformation that ultrasonic wave is carried out reconstruct that said ultrasonic wave reconstructed module (312) is passed through ultrasonic wave decomposing module (311) and linked to each other with data acquisition unit (2).
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