CN101353431B - Quasi-molecule laser preparing method for high conductive polyvinylidene fluoride material - Google Patents
Quasi-molecule laser preparing method for high conductive polyvinylidene fluoride material Download PDFInfo
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- CN101353431B CN101353431B CN2008102222237A CN200810222223A CN101353431B CN 101353431 B CN101353431 B CN 101353431B CN 2008102222237 A CN2008102222237 A CN 2008102222237A CN 200810222223 A CN200810222223 A CN 200810222223A CN 101353431 B CN101353431 B CN 101353431B
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Abstract
The invention relates to an excimer laser preparation method of high-conductive polyvinylidene fluoride material, belonging to the field of the mutual effect of laser and matter. The device comprises a laser, a beam homogenizing system, a second convergent component and a workbench which are sequentially arranged along the propagation direction of light, wherein, the beam homogenizing system comprises a first level lens array, a second level lens array and a first convergent component. When the high-conductive polyvinylidene fluoride material is prepared, collimation is carried out by He-Ne lasers and a light path is adjusted firstly so that the light path has complete light spot shape; and then the energy flow density of the material surface is controlled to be 44mJ/cm<2> to 112mJ/cm<2> by adjusting the size and the output energy of the laser spot; a sample is put on the workbench and the laser repetitive frequency is set, material radiation modification is carried out by starting the laser, and the modification is finished after the radiation of the number of overall pulses is finished, and laser output is stopped simultaneously. The invention causes the surface conductivity to be improved by 9 to 12 orders of magnitude, simultaneously, the prepared conducting polymer is more stable.
Description
Technical field
The present invention relates to a kind of excimer laser preparation method of high conductive polyvinylidene fluoride material, belong to the research field of laser and matter interaction.
Background technology
Laser surface treating technology is that an emerging technology is widely studied and applied in the metal solid field.Surface treatment at polymkeric substance is to report since the research first of nineteen eighty-two American I BM company.This technology is compared with other traditional modification technology (as chemical reagent processing, energetic ray radiation, plasma modification etc.), it is simple to have treatment process, facility investment is little, can keep the performance of body to obtain to be different from the advantages such as surface property of bulk properties simultaneously.Research through nearly 30 years acquires a great achievement in importances such as improving the wetting ability of polymer surfaces, dyeability, cohesiveness and electroconductibility.Wherein, preparation has the concern that the active polymkeric substance of high conduction is subjected to each research field always.
Conductivity of electrolyte materials (σ) is one of the widest physical properties of its numerical range, and σ is from 10
8(Ω cm)
-1To 10
-22(Ω cm)
-130 orders of magnitude have been comprised altogether.Utilize specific conductivity 10
-9～10
-2(Ω cm)
-1Material, can eliminate the static electric charge on man-made satellite, travelling belt and the sleeve pipe effectively; Greater than 10
-2(Ω cm)
-1Material, can be used to make the electromagnetic shielding material of forms such as coating or case; Greater than 10
- 1(Ω cm)
-1The surface conductivity material, can utilize it to make disk or the like.The specific conductivity of condition is all very little in most polymkeric substance.At present, the specific conductivity of the conductive polymers by prepared in various methods can reach semi-conductor or conductor scope, and its conductivity also can compare favourably with silver, copper.As the polyacetylene after mixing, polypyrrole, Polythiophene, poly-to benzene, polyaniline etc., specific conductivity all can reach 10
3(Ω cm)
-1More than.These polymer types all are the conjugated type materials, chemically are doped to the master simultaneously.But by discovering, there is less stable in this class conductive polymers, and doping and specific conductivity are disproportionate, and problem such as conducting process is indeterminate.These problems also hamper always conductive polymers further develop with and Application Prospect.Therefore, when this field needs to prepare high conducting polymer materials urgently, solve the stability of conductive polymers problem, exploration discovery auto-doping or plain conductive polymers promote " light conductor " to realize practicability early.
Summary of the invention
The present invention proposes a kind of preparation method who prepares high conductive polyvinylidene fluoride material.The conductive polymers that use a process for preparing is more stable, and 248nmKrF excimer laser energy density is at 44mJ/cm
2～112mJ/cm
2Between, make its surface conductivity improve 9～12 orders of magnitude, promptly 10
-13To 10
-1(Ω cm)
-1
To achieve these goals, the present invention has taked following technical scheme.This device is disposed with laser apparatus, all beam system 2, second positive lens 3 and be used to place the worktable 4 of sample along the propagation direction of light.Described equal beam system 2 comprises first step lens arra 8, second stage lens arra 9 and first positive lens 10 that sets gradually along the propagation direction of light.
The quasi-molecule laser preparing apparatus preparation method of high conductive polyvinylidene fluoride material, this method comprises the steps:
1) choosing PVDF (polyvinylidene fluoride material) film that thickness is not less than 0.5mm is specimen material, and adopts ultrasonic wave that it is cleaned;
2) temperature-sensitive paper is placed on the worktable 4, regulate the laser pulse repetition frequency of laser apparatus 1 and the position of worktable 4, make and on temperature-sensitive paper, obtain hot spot, and the position O at record worktable place this moment;
3) take off temperature-sensitive paper, calculate the size of hot spot; The laser that records O place, worktable position by resistance dynamometer is on average exported energy then, on average exports energy divided by the spot size on the temperature-sensitive paper with laser, obtains the laser energy density at O place, worktable position;
The value of described laser energy density is 44mJ/cm
2～112mJ/cm
2
4) the PVDF film after the ultrasonic cleaning is positioned over the position at temperature-sensitive paper place on the worktable 4, makes the PVDF film surface vertical, carry out laser irradiation with the laser propagation direction.
The present invention in 248nmKrF excimer laser energy density at 44mJ/cm
2～112mJ/cm
2Between, make its surface conductivity improve 9～12 orders of magnitude, promptly 10
-13To 10
-1(Ω cm)
-1, the conductive polymers that uses this method to prepare simultaneously is more stable.
Description of drawings
Fig. 1 is an excimer laser irradiator synoptic diagram of the present invention
Fig. 2 is a worktable front view among Fig. 1
Among the figure: 1, KrF excimer laser, 2, equal beam systems, 3, second assembles object lens, and 4, worktable, 5, laser beam, 6, sample, 7, hot spot, 8, first step lens arra, 9, second stage lens arra, 10, first positive lens.
Embodiment
The invention will be further described below in conjunction with accompanying drawing 1,2.
As shown in Figure 1, the excimer laser irradiation light path system that adopts in this enforcement mainly comprises laser apparatus 1, equal beam system 2, second positive lens 3 and worktable 4.All beam system 2 comprises the first step lens arra 8 that sets gradually along the propagation direction of light again, the second stage lens arra 9 and first positive lens 10.
Present embodiment adopts is the LPX305iF type excimer laser that German Lambda Physik company makes.Main performance index is as follows: excitation wavelength is 248nm, and pulsewidth is 20ns, and the maximum impulse energy is 1.2J/Pluse, and average output power is 60W, and repetition rate is 1～50Hz, and the output energy is 200～600mJ.The energy density of material surface is mainly controlled by laser output energy and spot size.
The laser irradiation method of modifying specifically carries out according to the following steps among the present invention:
The first step, the PVDF film of choosing thickness and be 0.5mm is a specimen material.Subsequently, adopt ultrasonic wave that it is cleaned.
Second step placed temperature-sensitive paper on the worktable, and the laser parameter of regulating laser apparatus is 1Hz, and pulse number is 1, obtained spot size and writing task platform 4 position coordinate O (x, y and z) on temperature-sensitive paper.
In the 3rd step, the laser that obtains O place, worktable 4 position by resistance dynamometer is on average exported energy.By the spot size that second step obtained, calculate the laser energy density at this place, be the energy density that the material surface place obtains.
The 4th step, PVDF film after the ultrasonic cleaning is placed the position (length of side of sample is not more than the hot spot length of side) at temperature-sensitive paper place on the worktable 4, and worktable 4 is placed O place, position, make the surface of PVDF film vertical with the laser propagation direction, carry out the operation of sample radiation modification, as shown in Figure 2.
The present invention is unlike the prior art, with quasi-molecule original beam 5 by one group of equal beam system 2 of lens arra after, converge to the radiation modification that carries out specimen material on the sample worktable 4 by second lens 3 again.Be evenly distributed by the light beam internal energy after the shaping, on worktable, obtain the length of side simultaneously, match, realize the control of specimen material surface energy density flow with the adjusting of laser technical parameters at the adjustable square focus spot 7 of 1～5cm.
Adopt the method in the present embodiment, present embodiment be described in detail below in conjunction with concrete testing data:
The residing work atmosphere of present embodiment belongs to air ambient, and the PVDF film sample thickness of choosing is 0.5mm; Material surface specific conductivity behind the irradiation is measured by SB100A/1 four point probe conductor/semiconductor resistivity measurement instrument, and calculation formula is σ=45.32 * (V/I), and wherein I is the electric current of film of flowing through, and V is the voltage that electric current produces when flowing through sample.
At first, collimate, adjust light path, make it have complete light spot shape by He-Ne laser; Then, by regulating laser facula size and output energy, control material surface energy flow density is 44mJ/cm
2～112mJ/cm
2Between; The PVDF film sample is fixed on the worktable, and it is 4Hz that laser repetition rate is set.After above step is finished, open laser, carry out the material irradiation modification, irradiation overall pulse number is finished modification after finishing, and laser stops output simultaneously, the data that specifically record as shown in Table 1:
As can be seen from Table 1, under the different-energy density, material surface is from producing conductive region to inactivation, total pulse number difference.Be that energy density is high more substantially, conductive region occurs more early, and inactivation also more early; With reducing of energy density, the specific conductivity of material surface increases, and its surface conductivity maximum value is energy density 44mJ/cm
2The time, σ is 4.20 * 10
-1(Ω cm)
-1
Following example 1,2 is respectively that energy density is 62mJ/cm
2And 92mJ/cm
2Regulate down the relation of material surface specific conductivity and laser pulse number.Wherein, the PVDF film thickness is 0.5mm, and laser repetition rate is 4Hz.
Behind the He-Ne Lasers collimation, temperature-sensitive paper is placed on the worktable, regulate operating position, making its facula area is 1.45 * 1.45=2.10cm
2, and record operating position coordinate this moment O.It is 250mJ that laser output energy is set, and by O place, resistance dynamometer measuring position energy, the acquisition average energy is 130mJ, and the laser energy decay is about 48%, and laser energy density is 62mJ/cm
2The PVDF film sample that is slightly less than facula area is placed position coordinates O place.It is 4Hz that laser pulse frequency is set.Be provided with under the different pulse numbers and open laser and carry out modification, pulse number is respectively 100,300,500,600,700,1500, respectively corresponding 1～No. 6 sample.Adopt four point probe to finish the measurement of surface conductivity to 6 samples after the modification.When pulse number was 100, considerable change appearred in laser and material surface effect sound, and this moment, conductive region appearred in material surface.But because the conductive region rate of diffusion is slower, scope is less can't be measured.When pulse number was 500, surface conductivity maximum value 1.2 * 10 appearred
-1(Ω cm)
-1Subsequently, specific conductivity descends to some extent, but keeps the bigger order of magnitude always.Experimental result sees Table 2.
Behind the He-Ne Lasers collimation, temperature-sensitive paper is placed on the worktable, regulate operating position, making its facula area is 1.45 * 1.45=2.10cm
2, and record position coordinate O.It is 350mJ that laser output energy is set, and by O place, resistance dynamometer measuring position energy, the acquisition average energy is 206mJ, and the laser energy decay is about 41%, and laser energy density is 98mJ/cm
2The PVDF film sample that is slightly larger than facula area is placed position coordinates O place.It is 4Hz that laser pulse frequency is set.Be provided with under the different pulse numbers and open laser and carry out modification, pulse number is respectively 100,150,200,300,400,500,600,700,800, and counter sample is 1～No. 9 respectively.Adopt four point probe to finish the measurement of surface conductivity to 9 samples after the modification.Experimental result sees Table 3.When pulse number was about 100, conductive region appearred.The conductive region diffusion is very fast, and when pulse number was 300, its surface conductivity was 4.00 * 10
-4(Ω cm)
-1With the increase of pulse number, surface conductivity increases.When maximum appears at pulse number and is 500, be 1.83 * 10
-3(Ω cm)
-1Subsequently, specific conductivity descends, and when pulse number was 800, the surface is inactivation because of serious carbonization.Experimental result sees Table 3.
For other energy density, can adopt in the same way and implement.
In sum, in the excimer laser irradiation polyvinylidene fluoride surface process, induce the conductive layer of one deck high conductivity on its surface.Laser energy density is at 44mJ/cm
2～112mJ/cm
2In the scope, producing maximum conductivity is 4.20 * 10
-1(Ω cm)
-1Adopt the prepared high conduction active polymer material of this method to belong to auto-doping or the type conducting polymer materials that undopes, broken through traditional conjugation pattern.Surface conductivity has increased by 12 orders of magnitude, makes it enter the conductor scope and becomes possibility.
Table 1
| Energy density (mJ/cm 2) | Produce pulse number (N) | Inactivation pulse number (N) | Specific conductivity maximum (Ω -1cm -1) |
| 112 | 50 | 400 | 3.74×10 -4 |
| 98 | 150 | 500 | 1.83×10 -3 |
| 92 | 150 | 600 | 8.64×10 -4 |
| 62 | 250 | - | 1.20×10 -1 |
| 44 | 300 | - | 4.20×10 -1 |
Table 2
| The sample sequence number | Pulse number (N) | Specific conductivity (Ω -1cm -1) |
| 1 | 100 | - |
| 2 | 300 | - |
| 3 | 500 | 1.2×10 -1 |
| 4 | 600 | 5.4×10 -2 |
| 5 | 700 | 7.5×10 -3 |
| 6 | 1500 | 2.6×10 -4 |
Table 3
| The sample sequence number | Pulse number (N) | Specific conductivity (Ω -1cm -1) |
| 1 | 100 | 0 |
| 2 | 150 | - |
| 3 | 200 | - |
| 4 | 300 | 4.00×10 -4 |
| 5 | 400 | 6.00×10 -4 |
| 6 | 500 | 1.83×10 -3 |
| 7 | 600 | 8.98×10 -4 |
| 8 | 700 | 7.14×10 -4 |
| 9 | 800 | 0 |
Claims (1)
1. the excimer laser preparation method of a high conductive polyvinylidene fluoride material, it is characterized in that: this method uses quasi-molecule laser preparing apparatus to be prepared, this quasi-molecule laser preparing apparatus comprises laser apparatus (1), also comprises the equal beam system (2), second positive lens (3) and the worktable (4) that set gradually along the propagation direction of light; Described equal beam system (2) comprises the first step lens arra (8) that sets gradually along the propagation direction of light, second stage lens arra (9) and first positive lens (10);
Utilize above-mentioned quasi-molecule laser preparing apparatus to prepare high conductive polyvinylidene fluoride material, its method comprises the steps:
1) choosing the PVDF film that thickness is not less than 0.5mm is specimen material, and adopts ultrasonic wave that it is cleaned;
2) temperature-sensitive paper is placed on the worktable (4), regulate the laser pulse repetition frequency of laser apparatus (1) and the position of worktable (4), make and on temperature-sensitive paper, obtain hot spot, and the position 0 at record worktable place this moment;
3) take off temperature-sensitive paper, calculate the size of hot spot; The laser that records 0 place, worktable position by resistance dynamometer is on average exported energy then, on average exports energy divided by the spot size on the temperature-sensitive paper with laser, obtains the laser energy density at 0 place, worktable position;
The value of described laser energy density is 44mJ/cm2～112mJ/cm2; When energy density was 112mJ/cm2, the laser pulse number that conductive layer produces was 50, and deactivated laser pulse number is 400; When energy density was 98mJ/cm2, the laser pulse number that conductive layer produces was 150, and deactivated laser pulse number is 500; When energy density was 92mJ/cm2, the laser pulse number that conductive layer produces was 150, and deactivated laser pulse number is 600; When energy density was 62mJ/cm2, the laser pulse number that conductive layer produces was 250; When energy density was 44mJ/cm2, the pulse number that conductive layer produces was 300;
4) with being positioned over the position that worktable (4) is gone up the temperature-sensitive paper place with the PVDF film after the ultrasonic cleaning in the step 1, make the PVDF film surface vertical, open laser, carry out laser irradiation with the laser propagation direction.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006074665A2 (en) * | 2005-01-12 | 2006-07-20 | Inverness Medical Switzerland Gmbh | A method of producing a microfluidic device and microfluidic devices |
| CN1861375A (en) * | 2006-06-16 | 2006-11-15 | 北京工业大学 | Method for preparing polyvinylidene fluoride conductive plastics |
| CN201272760Y (en) * | 2008-09-12 | 2009-07-15 | 北京工业大学 | Quasi-molecule laser production apparatus for high-conductivity kynoar material |
-
2008
- 2008-09-12 CN CN2008102222237A patent/CN101353431B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006074665A2 (en) * | 2005-01-12 | 2006-07-20 | Inverness Medical Switzerland Gmbh | A method of producing a microfluidic device and microfluidic devices |
| CN1861375A (en) * | 2006-06-16 | 2006-11-15 | 北京工业大学 | Method for preparing polyvinylidene fluoride conductive plastics |
| CN201272760Y (en) * | 2008-09-12 | 2009-07-15 | 北京工业大学 | Quasi-molecule laser production apparatus for high-conductivity kynoar material |
Non-Patent Citations (3)
| Title |
|---|
| 姬亚玲.激光辐射诱导PVDF导电性的研究.《中国激光》.2007,第34卷137-140. * |
| 荆涛.准分子激光微细加工光路变换的研究.《中国激光》.2002,第29卷592-594. * |
| 蒋毅坚.准分子激光辐照PVDF的拉曼和红外光谱研究.《光散射学报》.2008,第20卷(第2期),160-163. * |
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