CN1421565A - Normal-pressure low-temperature plasma treater for modifying fiber surface - Google Patents
Normal-pressure low-temperature plasma treater for modifying fiber surface Download PDFInfo
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- CN1421565A CN1421565A CN 02151229 CN02151229A CN1421565A CN 1421565 A CN1421565 A CN 1421565A CN 02151229 CN02151229 CN 02151229 CN 02151229 A CN02151229 A CN 02151229A CN 1421565 A CN1421565 A CN 1421565A
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Abstract
The present invention relates to one kind of medium-blocked discharge treater producing normal pressure low temperature plasma for fiber material modification. The treater consists of four parts including one pair of cooled planar discharge electrodes; two reaction gas ducts and two gas guide plates. The treater produces homogeneous low temperature plasma at atmosphere while avoiding interpolar arc light and spark discharge. Fiber material set in or passing through the discharge area is treated by the normal pressure and low temperature plasma to obtain effective modification. After the said treatment, the surface moistening performance and dyeing performance are improved obviously.
Description
Technical field:
The present invention relates to a kind of atmospheric low-temperature plasma treating apparatus, can avoid interelectrode arc light and spark discharge with this device or rather, under atmospheric pressure, produce homogeneous plasma by dielectric barrier discharge, make and leave standstill or handle through the normal pressure homogeneous plasma by the fibrous material in the region of discharge continuously, can obtain the active surface modification, the chemical fibre material modification of hydrophobicity becomes hygroscopic materials, and the dyeability of material also is significantly improved.Belong to the fibre modification field.
Background technology:
Dielectric barrier discharge is the method that produces low temperature plasma under atmospheric pressure, is widely used at present that ozone is synthetic, air and water purification handle, and makes aspects such as ultraviolet source, exciting gas laser device.For example: ZL99213572.9 and CN99115989.6 disclose a kind of low temperature plasma ozone generation flake and a kind of dielectric barrier discharge lamp respectively.Its principle is: between opposite electrode or electrode surface have dielectric layer, make between electrode discharge space produce plasma light beam or plasma gas.In the material modification field, carry out plasma polymerization at material surface under the low air pressure condition, can carry out modification to material surface handles, a kind of fabric plasma collating unit is disclosed as CN1259759 and ZL99218828.8, at input nitrogen, oxygen, produce low temperature plasma under the low vacuum condition, to fabric-modifying.Carry out the plasma material surface modifying treatment under these vacuum conditions, it is big to vacuumize energy consumption, and should not realize industrial continuous production.And CN1277267 discloses a kind of normal-pressure non-equilibrium plasma of metal surface enhanced usefulness, and it utilizes the super-high pressure pulse power supply to produce plasma under normal pressure, permeates the intensity that improves metal by force by ion.The temperature and the energy of the normal-pressure non-equilibrium plasma that this technology produces are too high, obviously can not be used for the surface modification of fiber textile material.Plasma device and the treatment technology method that can carry out the active surface modification to the fiber textile material under the exploitation condition of normal pressure, be suitable for and carry out industrialization and produce processing continuously, in order to improve the hygroscopicity of chemical fibre material, improve the wearability and the dyeability of chemical fibre material, have great market prospects.Regrettably still there is not the treating apparatus that utilizes dielectric barrier discharge to produce atmospheric low-temperature plasma so far, and the report that can carry out the active surface modification to fibrous material.
Summary of the invention:
The object of the invention is to provide a kind of atmospheric low-temperature plasma processor, this device is to utilize dielectric barrier discharge can avoid arc light and spark discharge to produce homogeneous plasma under atmospheric pressure, rest on or handle through the normal pressure homogeneous plasma by the fibrous material in the region of discharge continuously, can obtain the active surface modification.The chemical fibre material modification of hydrophobicity becomes hygroscopic materials.The dyeability of material is significantly increased simultaneously.
Another object of the present invention is to leave standstill or continuously by the method for region of discharge to the fibrous material surface modification with this processor processing.
Atmospheric low-temperature plasma processor provided by the present invention comprises a pair of plane discharge electrode with coolant cools, places two interelectrode two special media barrier plates, two reacting gas conduits and two gas guide boards.It is characterized in that:
(1) described processor is that two parts up and down by parallel placement constitute, every part all is the cuboid box that make with polytetrafluoroethylene (PTFE) or other withstand voltage insulating materials the side, processor is up and down on the parallel relative face of two parts, the middle part respectively cuts out a rectangle and seals with a special dielectric impedance plate, the processor middle slit of two parts two dielectric impedance plates up and down is plasma generation and handles the space, but processor the first half translation, to regulate suitable slot distances, can hold object being treated and leave standstill or pass through continuously.Slot distances is generally 1-5mm;
(2) placing two interelectrode two special media barrier plates, is the ceramic dielectric material plate of two surface finish.They weld respectively or are bonded on parallel two the relative surfaces of two parts up and down of plasma generation and processor.
(3) two plane discharge electrodes are separately fixed in two parts up and down of processor, are close to two dielectric impedance plates respectively, and isolated with the space of plasma generation and processing.This structure has avoided the electrode material of evaporation to be deposited on the pending thing effectively, avoid the metal deposition to pollute, two electrodes are cuboid cans of being made by stainless steel, copper or other metal (as brass, aluminium), polishing is wanted on the surface that can and dielectric impedance plate are close to, can links to each other with the circulate coolant cooling system with carrier pipe, and the cooling agent by the can of flowing through during discharge makes it cooling.
(4) processor respectively is provided with a gas conduit parallel with electrode in two parts up and down, and each vessel cover has out the channeling seam on the side of slit, and the reacting gas that flows out from the ditch seam transmits reacting gas (referring to accompanying drawing 2) through the gas flow guiding swash plate in slit.
(5) two blocks of dielectric-slabs are the ceramic dielectric material plate of handy surface finish such as silica, the ceramic wafer that contains Mg, Si
3N
4, Al
2O
3Deng, the plate that dielectric constant is bigger, thickness are too thin, and the ability of dielectric-slab opposing voltage will descend; When thickness was too thick, discharge voltage was too high, also was difficult to keep the uniformity consistency that discharges.Electrode and dielectric-slab need through polishing, and cooling electrode during discharge to avoid arc light and spark discharge, guarantees even discharge generation homogeneous plasma between dielectric-slab.
The external equipment of atmospheric low-temperature plasma processor provided by the invention comprises a high-frequency high-voltage origin system, a gas supply system and a cooling recirculation system.
Atmospheric low-temperature plasma processor provided by the present invention is with transformer oil or other high voltage bearing coolant cools, makes circulate coolant cool off two sparking electrodes by pump;
Atmospheric low-temperature plasma processor provided by the present invention, two plane discharge electrodes in addition high-frequency ac voltage be to supply with by commercially available high-frequency high-voltage origin system, its frequency is 5KHz-20KHz, voltage is greater than 3KV.According to fibrous material thickness adjusted frequency and the voltage for the treatment of modification, and in the discharge slit, pass to suitable discharge gas, can between two electrodes, produce gases used homogeneous plasma by the inboard middle discharge space of two dielectric barriers, and can avoid electric arc and spark discharge.
Another object of the present invention is implemented by following steps:
(1) according to being modified fibrous material characteristic and thickness adjusted slot distances;
(2) import continuously in order to produce the gas of plasma in the slit between two parts up and down to plasma processor; Reaction gas flow 2L/min-5L/min, gas are inert gases, inert gas and air, or the mist of inert gas and other gas such as nitrogen;
(3) add the high-frequency ac high pressure to two electrodes: in the frequency and voltage range of appropriate coupling, under suitable gas flow, can be between two dielectric impedance plates discharge generation normal pressure homogeneous plasma in the slit space, and can avoid arc light and spark discharge;
(4) rest in plasma generation and the processor discharge slit or fiber or the pending thing of fibre by slit continuously, after handling more than 10 seconds, can obtain the active surface modification.
The wettability improvement of handling back fiber or fibre is to confirm with following method:
Sample is tiled in colored solutions surface (5% potassium bichromate solution commonly used), the time of measuring the material complete wetting.Perhaps, the water droplet of 0.2cc is dripped to specimen surface, measure water droplet diameter or area at the circular wetting spot of specimen surface drawout in 20 seconds time.Obviously, atmospheric plasma body processor provided by the invention, can constitute easily and carry out the continuous process for producing device of industrial plasma, only need on the direction of advance of pending thing, several are set the invention provides plasma processor, guarantee that under certain material gait of march pending thing obtains enough processing times, and each plasma generation can use different reacting gas with processor, to obtain different treatment effects.
Advantage of the present invention also is conspicuous.Utilize the plasma processor and the using method of plane electrode dielectric barrier discharge provided by the invention, be easy to the various fiber textiles of large-area treatment, under the good situation of discharge scenario, not flashing or arc discharge, the ablation perforation and the pyrolytic damage of the object being treated of having avoided arc discharge and too high plasma temperature and having caused, the homogeneous plasma temperature and the energy of discharge generation are suitable, can be under the situation of not destroying fibrous inner structure character, make the chemical fibre material acquisition of hydrophobicity forever moisture-absorption modified, the wettability of fiber significantly improves.Under same dyeing condition, terylene (PET) coloration of textile materials performance improves a lot.
Sort processor can constitute normal atmosphere plasma continuous treater with external equipment and material transmission system, is used for suitability for industrialized production, is a kind of new technology of fiber material modification of energy-saving and environmental protection.
Description of drawings:
The structural representation of Fig. 1 atmospheric low-temperature plasma processor provided by the invention.
Figure a is a side view.Right-hand when handling continuously is charging aperture, and left is a discharging opening.
Figure b is the front view of processor discharging opening, and fiber or fabric processed when handling continuously outwards move from the lining.
Fig. 2 is the structural representation of Fig. 1 Lower Half.The first half structure is identical.Among the figure:
1-plasma generation and processor the latter half
2-plasma generation and processor the first half 3-top electrode dielectric-slab
4-bottom electrode dielectric-slab 5-top electrode 6-bottom electrode
The upper and lower gas guide board of 7-upper gas conduit 8-lower gas conduit 9-
10-material 11-electrode coolant feed pipe 12-air shooter
The upper surface of the latter half of 13-plasma processor
The latter half oblong openings of 14-plasma processor, fixing bottom electrode places in the oblong openings, and polished surface and bottom electrode dielectric-slab are close to
The channeling that goes out of 15-lower gas conduit stitches
The specific embodiment:
Below by specific embodiment, further set forth substantive distinguishing features of the present invention and obvious improvement, but the present invention only is confined to embodiment by no means.
Embodiment 1
Atmospheric low-temperature plasma processor among use Fig. 1 is weaved cotton cloth to terylene (polyethylene terephtalate) and is handled continuously.Two electrodes are brass, and the silica plate is as block media.Upper/lower electrode adds the ac high-voltage about about 10KHz, with argon gas or argon gas and Air mixing gas feed processor up and down the discharge slit between two parts as discharge gas, produce the bright aura of bluish violet at discharge space, and do not observe arc light and spark discharge.Argon flow amount is big more, and the aura of discharge space is bright more, and it is strong more to discharge.Distance is 3mm between the slit.
Woven dacron is statically placed in the discharge slit, or slowly by discharge slit several times, under the stable discharging situation, no matter static treatment or processing are continuously guaranteeing that the last treatment effect of woven dacron is identical under processing time the same terms.When handling about 2 minutes, ablation or perforation that pyrolytic damage or arc light and spark discharge cause are not observed in the then apparent no any variation of woven dacron yet.
Water droplet is hemispherical before handling on woven dacron, and auxilliary exhibition launches to be a circular moistening spot and drop in to assist immediately on the cotton.Handle back water droplet auxilliary immediately expansion on woven dacron, the auxilliary circular moistening spot diameter that launches reaches about 40mm after 20 seconds, and is identical with the cotton situation.
Dispersive red dye with same concentration dyes under identical dyeing condition, handles back sample and untreated samples comparison Color and obviously improves, and the color lightness improves approximately 12% under the best-case, and chroma improves about 23%.
This hygroscopic raising did not have obviously change at least in 1 year.The change of Color also is washable.
When treatment process condition is inappropriate, in discharge space, the wire discharge channel can occur, and the glow deepening, handle the about 0.5mm of diameter of sample can appear running through in the back sample at wire discharge channel place ablation pore, the quantity of these pores becomes 100cm with the inhomogeneity degradation of discharge
2Several at least on the area, tens up to a hundred at most, at this moment sample goes to pot.
Embodiment 2
Use plasma generation and processor among Fig. 1 that surface density is 170g/m
2PBT (polybutylene terephthalate (PBT)) melt-blowing nonwoven (melt spraying non-woven fabrics) carry out static state or handle continuously.Handle with the method that example 1 is roughly the same, but treatment conditions difference to some extent.Under the stable discharging situation, handle the apparent no any variation of back sample, do not observe ablation or perforation that pyrolytic damage or arc light and spark discharge cause yet.
The sample of PBT melt spraying non-woven fabrics cut-off footpath 5cm before and after handling, flat the assisting of nonwoven fabric sample is being 5% yellow potassium bichromate solution surface before handling, and nonwoven fabric is kept afloat nonwetting in 20 seconds; And the complete wetting at once in of the sample after handling less than 1 second time, the nonwoven fabric yellowing of white.
When treatment process condition is not good, the discharge deterioration phenomenon similar with example 1 also can appear, and sample equally also can ablatedly destroy.
Untreated sample is flat assisted in solution surface after 2 minutes, and to keep afloat nonwetting fully always; Untreated sample soaks the effect after 3 minutes in potassium bichromate solution, the material hygroscopicity is poor, and is not wetting, the basic no change of sample color; After producing the homogeneous plasma processing under the stable discharging situation, sample is tiled in the even variable color of solution surface moisture absorption at once.Handled under inhomogeneous weak discharge situation 8 minutes, sample is flat assists in the moisture absorption variable color of solution surface subregion, though wetting areas increase to some extent with handling time lengthening, but still inhomogeneous, and the phenomenon of boring a hole can appear in material.
Claims (8)
1, a kind of atmospheric low-temperature plasma treating apparatus that is used for fibre modification is characterized in that:
(1) the atmospheric low-temperature plasma processor that is provided comprises a pair of cooling agent, the plane discharge electrode of cooling.Put two interelectrode two special media barrier plates, two reacting gas conduits and two gas guide boards; The entire process device is that the two parts up and down by parallel placement constitute, every part all is the cuboid box that make with polytetrafluoroethylene (PTFE) or other withstand voltage insulating materials the side, processor is up and down on the parallel relative face of two parts, the middle part respectively cuts out a rectangle and seals with a special dielectric impedance plate, the processor middle slit of two parts two dielectric impedance plates up and down is plasma generation and handles the space, but processor the first half translation, to regulate suitable slot distances, can hold object being treated and leave standstill or pass through continuously;
(2) placing two interelectrode two special media barrier plates, is the ceramic dielectric material plate of two surface finish, and they weld or be bonded in plasma generation and processor respectively up and down on parallel two the relative surfaces of two parts;
(3) two plane discharge electrodes are separately fixed in two parts up and down of processor, are close to two dielectric impedance plates respectively, and isolated with plasma generation and processing space;
(4) processor respectively is provided with a gas conduit parallel with electrode in two parts up and down, and each vessel cover has out the channeling seam on the side of slit, and the reacting gas that flows out from the ditch seam transmits reacting gas through the gas flow guiding swash plate in slit.
2, by the described atmospheric low-temperature plasma treating apparatus that is used for fibre modification of claim 1, it is characterized in that described processor up and down the slot distances in the middle of two parts two dielectric impedance plates be 1-5mm.
3, by the described atmospheric low-temperature plasma treating apparatus that is used for fibre modification of claim 1, it is characterized in that described two electrodes are cuboid cans of being made by stainless steel, copper, brass or aluminium, the surface finish that can and dielectric impedance plate are close to, can links to each other with the circulate coolant cooling system with carrier pipe, and the cooling agent by the can of flowing through during discharge makes it cooling.
4,, it is characterized in that described dielectric impedance plate is the silica of surface finish, siliceous ceramic wafer, Si by claim 1 or the 3 described atmospheric low-temperature plasma treating apparatus that are used for fibre modification
3N
4, Al
2O
3Plate.
5, by the described atmospheric low-temperature plasma treating apparatus that is used for fibre modification of claim 1, the external equipment that it is characterized in that described atmospheric low-temperature plasma processor comprises a high-frequency high-voltage origin system, a gas supply system and a cooling recirculation system.
6, by the described atmospheric low-temperature plasma treating apparatus that is used for fibre modification of claim 1, it is characterized in that described cooling agent is a transformer oil.
7, by the described atmospheric low-temperature plasma treating apparatus that is used for fibre modification of claim 5, it is characterized in that the frequency of described high-frequency and high-voltage is 5-20KHZ, voltage is greater than 3KV.
8, handle by the described atmospheric low-temperature plasma treating apparatus that is used for fibre modification of claim 1 and leave standstill or, it is characterized in that concrete steps are continuously by the method for discharge to fibre modification:
(1) according to being modified fibrous material characteristic and thickness adjusted slot distances;
(2) import continuously in order to produce the gas of plasma in the slit between two parts up and down to plasma processor; Inert gas in the reaction gas flow 2L/min-5L/min, gas, indifferent gas and air or inert gas and other gas such as nitrogen or mist;
(3) add the high-frequency ac high pressure to two electrodes: in the frequency and voltage range of appropriate coupling, under suitable gas flow, discharge generation normal pressure homogeneous plasma in the slit space between two dielectric impedance plates, and avoid arc light and spark discharge;
(4) rest in plasma generation and the processor discharge slit or fiber or the pending thing of fibre by slit continuously, after handling more than 10 seconds, can obtain effective surface modification.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021512299A CN1190544C (en) | 2002-12-12 | 2002-12-12 | Normal-pressure low-temperature plasma treater for modifying fiber surface |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021512299A CN1190544C (en) | 2002-12-12 | 2002-12-12 | Normal-pressure low-temperature plasma treater for modifying fiber surface |
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| CN1421565A true CN1421565A (en) | 2003-06-04 |
| CN1190544C CN1190544C (en) | 2005-02-23 |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1293255C (en) * | 2004-03-04 | 2007-01-03 | 苏州丝绸科学研究所有限责任公司 | Plasma fabric treatment machine |
| WO2009100616A1 (en) * | 2008-02-04 | 2009-08-20 | Inano Limited | Atmospheric pressure plasma creating device |
| CN101481871B (en) * | 2008-12-29 | 2011-02-09 | 南通三信塑胶装备科技有限公司 | Energy-saving environment friendly low temperature normal atmosphere plasma continuous treater |
| CN102241392A (en) * | 2010-05-13 | 2011-11-16 | 宜兴市东成陶瓷有限公司 | Ceramic totally-closed ozone generating device |
| CN102390069A (en) * | 2011-10-28 | 2012-03-28 | 南京林业大学 | Atmospheric-pressure and low-temperature plasma continuous treatment device of wooden thin plates |
| CN101584026B (en) * | 2007-01-17 | 2012-11-14 | 朗姆研究公司 | Apparatuses for adjusting electrode gap in capacitively-coupled RF plasma reactor |
| CN102869180A (en) * | 2012-02-02 | 2013-01-09 | 中国印刷科学技术研究所 | Barrier discharge plasma surface treatment system for large-breath medium |
| CN103046307A (en) * | 2013-01-15 | 2013-04-17 | 上海工程技术大学 | Method for improving water-absorbing quality of kawo kawo fibers by plasma treatment |
| CN103242679A (en) * | 2013-05-20 | 2013-08-14 | 南通市争妍颜料化工有限公司 | Device for loading groups on surfaces of pigment particles and application of device |
| CN103451911A (en) * | 2013-08-16 | 2013-12-18 | 马鞍山谊腾亿纺织装饰用品有限公司 | Pretreatment process for spinning of kapok loose fibers |
| CN104161584A (en) * | 2014-08-05 | 2014-11-26 | 中国人民解放军总医院 | Novel low-temperature plasma operation device |
| CN105839388A (en) * | 2016-04-26 | 2016-08-10 | 江南大学 | Processing device for enhancing static electricity of fabric and working method |
| CN106192294A (en) * | 2016-07-29 | 2016-12-07 | 东华大学 | A kind of fast method for assisting daily dirt to remove |
| CN106245312A (en) * | 2016-08-31 | 2016-12-21 | 南京苏曼等离子科技有限公司 | Normal atmosphere low temperature plasma continuous tow arrangement in fibre process and processing method |
| CN106272783A (en) * | 2016-09-22 | 2017-01-04 | 安徽三和工艺品有限公司 | A kind of Fructus Jujubae wood does old processing method |
| CN110761067A (en) * | 2019-10-30 | 2020-02-07 | 中国人民解放军空军工程大学 | Carbon fiber surface continuous treatment method and device based on normal-pressure DBD discharge |
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2002
- 2002-12-12 CN CNB021512299A patent/CN1190544C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1293255C (en) * | 2004-03-04 | 2007-01-03 | 苏州丝绸科学研究所有限责任公司 | Plasma fabric treatment machine |
| CN101584026B (en) * | 2007-01-17 | 2012-11-14 | 朗姆研究公司 | Apparatuses for adjusting electrode gap in capacitively-coupled RF plasma reactor |
| WO2009100616A1 (en) * | 2008-02-04 | 2009-08-20 | Inano Limited | Atmospheric pressure plasma creating device |
| CN101481871B (en) * | 2008-12-29 | 2011-02-09 | 南通三信塑胶装备科技有限公司 | Energy-saving environment friendly low temperature normal atmosphere plasma continuous treater |
| CN102241392A (en) * | 2010-05-13 | 2011-11-16 | 宜兴市东成陶瓷有限公司 | Ceramic totally-closed ozone generating device |
| CN102241392B (en) * | 2010-05-13 | 2013-04-17 | 宜兴市东成陶瓷有限公司 | Ceramic totally-closed ozone generating device |
| CN102390069A (en) * | 2011-10-28 | 2012-03-28 | 南京林业大学 | Atmospheric-pressure and low-temperature plasma continuous treatment device of wooden thin plates |
| CN102390069B (en) * | 2011-10-28 | 2014-06-04 | 南京林业大学 | Atmospheric-pressure and low-temperature plasma continuous treatment device of wooden thin plates |
| CN102869180A (en) * | 2012-02-02 | 2013-01-09 | 中国印刷科学技术研究所 | Barrier discharge plasma surface treatment system for large-breath medium |
| CN103046307B (en) * | 2013-01-15 | 2015-01-28 | 上海工程技术大学 | Method for improving water-absorbing quality of kawo kawo fibers by plasma treatment |
| CN103046307A (en) * | 2013-01-15 | 2013-04-17 | 上海工程技术大学 | Method for improving water-absorbing quality of kawo kawo fibers by plasma treatment |
| CN103242679A (en) * | 2013-05-20 | 2013-08-14 | 南通市争妍颜料化工有限公司 | Device for loading groups on surfaces of pigment particles and application of device |
| CN103451911A (en) * | 2013-08-16 | 2013-12-18 | 马鞍山谊腾亿纺织装饰用品有限公司 | Pretreatment process for spinning of kapok loose fibers |
| CN104161584A (en) * | 2014-08-05 | 2014-11-26 | 中国人民解放军总医院 | Novel low-temperature plasma operation device |
| CN104161584B (en) * | 2014-08-05 | 2017-08-08 | 中国人民解放军总医院 | New low-temperature plasma operation device |
| CN105839388A (en) * | 2016-04-26 | 2016-08-10 | 江南大学 | Processing device for enhancing static electricity of fabric and working method |
| CN106192294A (en) * | 2016-07-29 | 2016-12-07 | 东华大学 | A kind of fast method for assisting daily dirt to remove |
| CN106245312A (en) * | 2016-08-31 | 2016-12-21 | 南京苏曼等离子科技有限公司 | Normal atmosphere low temperature plasma continuous tow arrangement in fibre process and processing method |
| CN106245312B (en) * | 2016-08-31 | 2018-05-01 | 南京苏曼等离子科技有限公司 | Normal atmosphere low temperature plasma continuous tow arrangement in fibre process and processing method |
| CN106272783A (en) * | 2016-09-22 | 2017-01-04 | 安徽三和工艺品有限公司 | A kind of Fructus Jujubae wood does old processing method |
| CN110761067A (en) * | 2019-10-30 | 2020-02-07 | 中国人民解放军空军工程大学 | Carbon fiber surface continuous treatment method and device based on normal-pressure DBD discharge |
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