常压等离子体辅助去除磷酸酯淀粉和聚乙烯醇混合浆料的研究
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摘要
在纺织工业中,淀粉及其改性淀粉、聚乙烯醇(PVA)和聚丙烯酸酯是常用几种浆料。上浆织物必须要经过退浆工序来满足后道加工(染色、印花和后整理)的要求。传统的退浆是利用热的烧碱溶液来完成退浆,但是这种方法产生的废液pH值较高,且废液必须经过漂洗和中和,所以会造成水资源的大量浪费,产生较高的能耗。据有关报道,纺织工业每年排放污水达到9亿多吨。此外,过度的碱液退浆还会造成纤维的损伤。这对环境造成了严重的污染,不符合当今环保的要求,不利于纺织工业的可持续发展。要彻底解决这个问题,需要对原有的纺织后整理工艺路线进行改进。
等离子体技术与传统化学处理相比,不需要水和化学试剂,大大减少了环境污染和污水处理成本。它是一种环境友好型的技术,同时该处理方法不会对纺织品的主体性能产生影响。作为一种高效的表面改性技术,等离子体技术在纺织品预处理和退浆等方面的应用越来越受到关注因此,将等离子体技术应用到纺织工业的退浆过程中,不仅能大大减少化学药品的用量和污水的排放,还能降低能耗和减少用水量,具有重大的环境效益和经济效益。
然而,过去大量得研究主要集中在低压等离子体对纺织品的处理方面。低压等离子体需要一个昂贵的真空系统,这样导致其不能对样品进行连续处理。与低压等离子体相比,常压等离子体不需要真空系统,可实现在线的连续化处理样品。此外,常压等离子体中的电子温度要比低压等离子体低得多。因此,常压等离子体特别适合应用到对温度敏感的基体处理。同时,常压等离子体处理能将大量的化学活性基团引入到基体表面,进而改善基体的润湿性能、印染性能、粘结性能等。利用常压等离子体处理纺织品时等离子体和纺织品之间的相互作用与低压等离子的情况是不同的。在常玉下,尤其是喷射式常压等离子体系统,等离子体是在一个喷头中产生后向外喷射而形成等离子体射流,然后和被处理基体接触完成处理过程。因此,喷头与基体间距离、处理时间、气体成份及流速等因素对处理效果有着显著影响。此外,由于在常压等离子体处理过程中,基体是置于外界大气环境中,会吸收空气中的水分而使材料具有一定的回潮率。水分的存在使得等离子体和被处理基体间的相互作用变得更为复杂,对等离子体的处理效果产生一定的影响。
等离子体退浆的研究大多集中在单一的浆料上(如PVA浆料),而对混合浆料及与传统退浆方法相结合退浆的报道较少。因此本课题采用实验室中常压等离子体射流(APPJ)装置,从混合浆料膜到混合浆上浆织物系统地研究了常压等离子体射流预处理对NaHCO3退浆、超声波退浆相结合对织物退浆效果的影响,并探讨了等离子体处理参数和织物含湿量对浆膜刻蚀、表面形态的影响。通过一系列的表面分析测试方法,如扫描电子显微镜(SEM)、院子力显微镜(AFM)以及X射线光电子能谱(XPS)等标面形态和化学分析方法测试了经等离子体处理前后,浆膜表面发生的物理和化学的变化。通过测量浆膜和上浆织物的刻蚀失重率及其退浆率来分析等离子体处理直接去除浆料和对后道退浆效果的影响。通过芯吸高度的变化来表征处理后织物的润湿性。
首先,本文研究了He/O2常压等离子体处理参数(时间、喷头与薄膜距离和流量)对磷酸酯淀粉和聚乙烯醇(PVA)混和浆料膜表面的刻蚀及形态的影响。研究发现随着处理时间的延长和氧气流量的增加,浆膜的失重率、表面粗糙度和表面积增加,但处理时间超过45s后,失重率的增量放缓。随着喷头与浆膜距离的增加,浆膜的失重率、表而粗糙度和表面积先增加后减小。当处理距离超过6mm,处理效果几乎为0,而当距离为2mm时,处理效果最佳。研究还发现,等离子体处理使得大量的含氧活性基团引入到浆膜表而,提高了浆料的亲水性
其次,为了研究磷酸酯淀粉和聚乙烯醇(PVA)混和浆膜含湿量对等离子体处理的影响,三组浆膜分别在相对湿度为10%、65%和97%的环境中平衡24小时,对应样品的回潮率分别为3.2%、10.5%和79.2%,然后经等离子体处理不同时间,研究浆膜含湿对等离子体刻蚀的影响。随后研究了浆膜不同含湿量对等离子体退浆效果的影响。原子力显微镜(AFM)测试结果发现,经等离子体处理后,样品表面的粗糙度值均有了明显提高。随着含湿量得增加,粗糙度呈现出先增加后减小的趋势。当处理环境的相对湿度丛10%增加到65%时,浆膜表面粗糙度从16.01mm增加到16.62nm。当处理环境相对湿度增加到97%时,浆膜表面粗糙度降低到13.59nm。失重率结果表明,随着含湿量得增加,经等离子体处理后,失重率增加,但与粗糙度结果相比,可以看出,在一定条件下,两者并没有直接的联系,也就是说等离子体处理过程中,高的刻蚀率不一定能产生较粗糙的基体表面。退浆结果显示,随着等离子体处理时间的延长,所有样品的退浆率增加。并且,随着含湿量的增加,退浆率是在降低的。当在10%RH下处理,样品经过20min退浆的退浆率最大,达到96%左右。而当相对湿度达到最大值97%时,样品的退浆率最小,为90%左右。
为了研究等离子体处理对传统化学退浆的影响,利用He/O2常压等离子体射流(APPJ)对混合浆料上浆的织物进行预处理,随后在NaHCO3溶液中进行退浆。AFM测试结果表明,经等离子体处理后,上浆织物表而变得粗糙。未处理样品和等离子体处理15s、45s后,表面平均粗糙度分别为2.2,8.9和26.8nm,粗糙度均方根分别为2.8,11.4和33.1nm。XPS测试表明,经等离子体处理后,上浆织物表面的化学成分发生了显著变化。样品表面的氧含量显著增加,说明大量的含氧活性基团引入到表面,增加了浆料的亲水性。退浆率结果显示,等离子体预处理大大的提高了NaHCO3退浆的效率.随着等离子体处理时间的增加,碱退浆率显著增加。对于未经等离子体处理的样品,碱退浆率仅为77%,而经等离子体处理45s后,随后进行相同工艺的碱退浆,退浆率可以达到95%以上。同时,等离子体预处理可以在一定程度上减小碱退浆的温度,并显著地缩短碱退退浆的时间。
为了研究等离子体预处理对超声波退浆的影响,利用等离子体对混合浆料上浆的织物进行预处理,随后在超声波环境下进行退浆。随着等离子体处理时间的延长,上浆织物表面的粗糙度增加,并且有大量的亲水极性基因引入到织物表面。退浆试验结果表明,仅仅使用超声波,退浆效果基本没有。但仅通过等离子体处理就可在80℃下获得大约95%退浆率。然而,等离子体与超声波联合退浆,可在较低的温度下实现较高的退浆率。经等离子体处理50s后,再在60℃下经20分钟超声波退浆,退浆率可达到98%以上,并且随着等离子体处理时间的增加,超声波退浆率增加。此外,与仅通过等离子体退浆的试样相比,等离子体和超声波联合退浆的试样的芯吸高度分别增加了9.7%,12.9%,15.1%和10.1%。芯吸高度的增加表明等离子体和超声波联合处理能够有效去除棉织物表面的绝大部分浆料,提高了退浆效率。
在研究等离子体预处理对传统去除磷酸酯淀粉和聚乙烯醇(PVA)混合浆料后,本论文又研究了等离子体处理对NaHCO3去除涤纶织物上聚丙烯酸酯浆料的影响。AFM测试结果表明,随着等离子体处理时间的增加,聚丙烯酸酯浆料表面粗糙度显著增加。对于未经处理、35s处理和50s处理得薄膜,表面粗糙度(Ra)值分别为0.93,9.15和15.97nm。同时,浆料表面的氧含量也得到了大大提高,大量的亲水性基团C-O-H、 O=C-O在浆料表面生产,提高了聚丙烯酸酯浆料的亲水性。失重率结果显示,随着等离子体处理时间的延长,失重率增加。但当处理时间超过50s后,失重率的增量放缓。退浆结果显示,随着氦/氧气等离子体处理时间的增加,湿退浆的退浆率有了显著提高。经过65s的等离子体预处理,随后在经过5min的湿处理,退浆率可以达到99%以上。然面,在相同的湿退浆条件下,对于没有经过预处理的面料,退浆率仅有28%左右。此外,退浆率随着退浆温度和时间的增加面增大。等离子体处理不能明显的降低湿退浆温度,但能显著地减少退浆时间。
In the textile industry, many starches and modified starches, polyvinyl alcohol (PVA) and polyacrylate are widely used as sizing agent for fabric. But sized fabrics have to be desized to meet the subsequent processing (dyeing, printing and finishing). In conventional desizing processes, the sized fabrics are washed with hot water and NaOH to remove size agents. Because of the high pH values in this method, the treatment should be followed by intensive rinsing and neutralizing, which means that large amount of water and energy is also consumed. The status shows that about900millions tons of waste water is used every year in textile industry. Moreover, the aggressive scouring treatment conditions frequently damage the fiber. Obviously, this desizing process is unable to meet the requirement of environmental protection and quite adverse to the sustainable development of textile industry. Therefore, in order to deal with the problems, the processing route of desizing and finishing needs to be improved.
Compared with the conventional chemical processes, plasma treatment does not require the use of water and chemicals, resulting in the drastic reduction in pollutants and a corresponding cost reduction for effluent treatment. Plasma treatment is an environmentally friendly technique without affecting the bulk properties of textiles. As a high-efficiency surface modification technology, more and more researchers pay close attention to the application of plasma treatment in the pre-treatment and finishing of textiles. If plasma technology can be applied in textile desizing process, both chemical agents and wastewater will be significantly reduced. Meanwhile, the consumption of energy and water can be greatly decreased. Therefore, it has great environmental and economical benefits.
However, previously study mostly focused on the treatment of low-pressure plasma to textiles. The low-pressure plasma involves a vacuum system and thus may not be continuous processes. Compared with low-pressure plasma, the atmospheric pressure plasma treatments do not require a vacuum system and therefore can be applied on-line for substrates. And it is not doubtable that the electron temperature is much lower in the atmospheric pressure plasma in comparison to the typical low-pressure reactor, therefore they are particularly suited to apply to textile processing because most textile materials are heat sensitive polymers. In addition, it is a versatile technique, where a large variety of chemically active functional groups can be incorporated into the textile surface. The possible aims of this are improved wettability, adhesion of coatings, printability, induced hydro-and/or oleophobic properties, changing physical and/or electrical properties, cleaning or disinfection of fiber surfaces etc. But, there is difference in interaction of plasma and textiles between low and atmospheric pressure. At atmospheric pressure, especially for atmospheric pressure plasma jet, plasma is generated in noddle and ejects to form plasma jet, then reaches onto the surface of the materials. So, the plasma treatment parameters, such as the distance between noddle and material, treatemt time, component and flow velocity of gas, etc., influence the plasma treatment effect. Moreover, because the atmospheric pressure plasma treatment is in atmosphere, the substrate material may absorb significant amount of water. The existence of water molecules can lead to a more complicated interaction between active species in plasma and substrate surface
The previously study of plasma desizing mostly focused on the removal of the single size agent (such as PVA). and up to now, there are few report about plasma desizing blended size and combination of plasma and traditional desizing method. Therefore, the objective of this study is to investigate the influence of plasma-wet treatment on desizing of sized fabrics with blended size agent by atmospheric pressure plasma jet (APPJ), andi studied the influence of plasma treatment parameters and moisture content in fabric on plasma etching and surface morphological of size film. Morphological and chemical changes on the fabric surface are characterized by Scanning Electron Microscope (SEM), Atomic force Microscope (AFM) and X-ray Photoelectron Spectra (XPS), respectively. My measurement of weight loss and percent desizing rate lo discuss and analyse the inlluence of plasma treatment on plasma directly removal of size and on subsequence wet desizing effect. The wettability of desized fabric is characterized by wicking height.
Firstly, the inlluence of different processing parameters (treatment lime, jet to substrate distance and gas flow rale) on the etching effect and surface morphology of blended size film of phosphate starch and PVA by He/O2atmospheric pressure plasma jet (APPJ). The results show that as the increase of treatment time and O2flow rate, the weight loss, surface roughness and surface area of size film increase. But, after treatment time is over45s, the increment of weight loss decreases. Moreover, the weight loss, surface roughness and surface area of size film increase firstly and then decrease as the jet to substrate distance increases. When the distance is over6mm, there almost are no treatment effect on the surface, but when the distance is2mm, the best treatment effect can be observed. The research results also show that plasma treatment can introduce more oxygen-contained active groups onto the size film surface, which improve the hydrophilcity of blended size.
Secondly, to investigate the relationship between the absorbed moisture and plasma treatment effect, atmospheric pressure plasma jet (APPJ) is used to treat the blended size film of phosphate starch and PVA with moisture regain (MR) of3.2%、10.5%and79.2%corresponding to10%、65%and97%relative humidity (RH), respectively. Atomic Force Microscope (AFM) result shows that after plasma treatment, the surface roughness of all three group samples obviously increase. As the increase of absorbed moisture, the surface roughness increase firstly and then decrease. When increase the RH from10%to65%. the surface roughness increase from16.01nm to16.62nm. But further increase RH to97%. the roughness is only13.59nm. The weight loss result indicates that the weight loss increase as the increase of absorbed moisture. But compared with surface roughness, there is no direct relation between weight loss and roughness under certain conditions, that is higher etching rate may be not result in rougher surface after plasma treatment. The desizing results show that as the increase of plasma treatment, the percent desizing rale (PDR) increase for the all samples. And the PDR decrease as the increase of absorbed moisture of blended size. When plasma treatment is under10%RH, the PDR is the biggest, about96%. But when RH is97%. the PDR is only about90%.
To investigate the influence of plasma treatment on conventional wet desizing. the sized fabrics are treated by He/O2atmospheric pressure plasma jet (APPJ). subsequently the treated fabrics are desized by NaHCO3. AFM analysis shows that the surfaces of sized fabrics become rougher after plasma treatment. The Ra values were2.2.8.9and26.8nm and the Rms values were2.8,11.4and33.1nm for untreated, the plasma treated for15and45s. respectively. XPS analysis indicates that the surface chemical composition of sized fabrics is greatly changed after plasma treatment. Compared to the untreated, the oxygen content increased significantly indicating oxygen containing polar groups introduced onto the surface after He/O2plasma exposure, which improves the hydrophilicity of blended size. The desizing results show that plasma pre-treatment significantly improves the NaHCO3desizing effect. As the increase of plasma treatment time, the percent desizing rate of NaHCO3increases. Only about77%PDR could be reached for the untreated fabrics, whereas more than95%PDR was achieved after45s plasma treatment followed by the same NaHCO3desizing process. Plasma pre-treatment can decrease the NaHCO3desizing temperature to some extent, and significantly shorten NaHCO3desizing time.
To investigate the influence of plasma pre-treatment on ultrasound desizing, the sized fabrics with blended size is treated by APPJ, and subsequently the treated fabric is desized by ultrasound. As the increase of plasma treatment time, the surface of sized fabric becomes rougher, and more oxygen-containing polar groups are introducted onto the surface of fabric. The desizing results show that only ultrasound treatment almost can not remove the size from fabric surface. But, only plasma treatment can observe about95%PDR at80°C. However, the combination of plasma and ultrasound can observe higher PDR at lower desizing temperature. The PDR reached98.3%for the fabrics with50s plasma treatment followed by ultrasound desizing at60°C for20min. And as the increase of plasma treatment time, the PDR of ultrasound treatment increase. Moreover, compared with the samples with plasma treatment only, the relative increase of the capillary height of the fabrics desized by the plasma-ultrasound were9.7%.12.9%.15.1%and10.1%. respectively. The increase of capillary heights indicated that plasma treatment followed by the ultrasound desizing could effectively remove most of the blended size on cotton fabrics
Finally, the relationship between APPJ and NaHCO3removing polyacrylate sixes from PET fabric is also studied. AFM analysis shows that the surfaces became progressively rougher after the plasma treatment. The Ra values are0.93,9.15and15.97nm for the untreated sample, the plasma treated for35and50s. respectively. And compared to the untreated sample, the O/C ratios for all two plasma-treated fabrics increased dramatically with an increase of treated time suggesting that oxidation occurred and a higher level of oxygen-based functional groups (C-O-H, O=C-O)were formed on the surface exposed to He/O2APPJ. The increase of these polar groups is responsible for the higher hydrophibilily of the polyaerylate size. The weight loss result indicates that the weight loss increased with an increase of plasma treatment time. Hlowever, after50s exposure time, the increment of weight losses slow down. The desizing results show that as the helium/oxygen plasma treatment time increase, the PDR has a significant increase after wet desizing. More than99%PDR was achieved after65s plasma treatment followed by a5min wet desizing, whereas only about28%PDR can be reached for the untreated fabrics. Moreover, the PDR of the all samples increases with the increase of wet desizing temperature and time. Meanwhile plasma treatment can not observably decrease desizing temperature but dramaticlly reduce desizing time.
等离子体技术与传统化学处理相比,不需要水和化学试剂,大大减少了环境污染和污水处理成本。它是一种环境友好型的技术,同时该处理方法不会对纺织品的主体性能产生影响。作为一种高效的表面改性技术,等离子体技术在纺织品预处理和退浆等方面的应用越来越受到关注因此,将等离子体技术应用到纺织工业的退浆过程中,不仅能大大减少化学药品的用量和污水的排放,还能降低能耗和减少用水量,具有重大的环境效益和经济效益。
然而,过去大量得研究主要集中在低压等离子体对纺织品的处理方面。低压等离子体需要一个昂贵的真空系统,这样导致其不能对样品进行连续处理。与低压等离子体相比,常压等离子体不需要真空系统,可实现在线的连续化处理样品。此外,常压等离子体中的电子温度要比低压等离子体低得多。因此,常压等离子体特别适合应用到对温度敏感的基体处理。同时,常压等离子体处理能将大量的化学活性基团引入到基体表面,进而改善基体的润湿性能、印染性能、粘结性能等。利用常压等离子体处理纺织品时等离子体和纺织品之间的相互作用与低压等离子的情况是不同的。在常玉下,尤其是喷射式常压等离子体系统,等离子体是在一个喷头中产生后向外喷射而形成等离子体射流,然后和被处理基体接触完成处理过程。因此,喷头与基体间距离、处理时间、气体成份及流速等因素对处理效果有着显著影响。此外,由于在常压等离子体处理过程中,基体是置于外界大气环境中,会吸收空气中的水分而使材料具有一定的回潮率。水分的存在使得等离子体和被处理基体间的相互作用变得更为复杂,对等离子体的处理效果产生一定的影响。
等离子体退浆的研究大多集中在单一的浆料上(如PVA浆料),而对混合浆料及与传统退浆方法相结合退浆的报道较少。因此本课题采用实验室中常压等离子体射流(APPJ)装置,从混合浆料膜到混合浆上浆织物系统地研究了常压等离子体射流预处理对NaHCO3退浆、超声波退浆相结合对织物退浆效果的影响,并探讨了等离子体处理参数和织物含湿量对浆膜刻蚀、表面形态的影响。通过一系列的表面分析测试方法,如扫描电子显微镜(SEM)、院子力显微镜(AFM)以及X射线光电子能谱(XPS)等标面形态和化学分析方法测试了经等离子体处理前后,浆膜表面发生的物理和化学的变化。通过测量浆膜和上浆织物的刻蚀失重率及其退浆率来分析等离子体处理直接去除浆料和对后道退浆效果的影响。通过芯吸高度的变化来表征处理后织物的润湿性。
首先,本文研究了He/O2常压等离子体处理参数(时间、喷头与薄膜距离和流量)对磷酸酯淀粉和聚乙烯醇(PVA)混和浆料膜表面的刻蚀及形态的影响。研究发现随着处理时间的延长和氧气流量的增加,浆膜的失重率、表面粗糙度和表面积增加,但处理时间超过45s后,失重率的增量放缓。随着喷头与浆膜距离的增加,浆膜的失重率、表而粗糙度和表面积先增加后减小。当处理距离超过6mm,处理效果几乎为0,而当距离为2mm时,处理效果最佳。研究还发现,等离子体处理使得大量的含氧活性基团引入到浆膜表而,提高了浆料的亲水性
其次,为了研究磷酸酯淀粉和聚乙烯醇(PVA)混和浆膜含湿量对等离子体处理的影响,三组浆膜分别在相对湿度为10%、65%和97%的环境中平衡24小时,对应样品的回潮率分别为3.2%、10.5%和79.2%,然后经等离子体处理不同时间,研究浆膜含湿对等离子体刻蚀的影响。随后研究了浆膜不同含湿量对等离子体退浆效果的影响。原子力显微镜(AFM)测试结果发现,经等离子体处理后,样品表面的粗糙度值均有了明显提高。随着含湿量得增加,粗糙度呈现出先增加后减小的趋势。当处理环境的相对湿度丛10%增加到65%时,浆膜表面粗糙度从16.01mm增加到16.62nm。当处理环境相对湿度增加到97%时,浆膜表面粗糙度降低到13.59nm。失重率结果表明,随着含湿量得增加,经等离子体处理后,失重率增加,但与粗糙度结果相比,可以看出,在一定条件下,两者并没有直接的联系,也就是说等离子体处理过程中,高的刻蚀率不一定能产生较粗糙的基体表面。退浆结果显示,随着等离子体处理时间的延长,所有样品的退浆率增加。并且,随着含湿量的增加,退浆率是在降低的。当在10%RH下处理,样品经过20min退浆的退浆率最大,达到96%左右。而当相对湿度达到最大值97%时,样品的退浆率最小,为90%左右。
为了研究等离子体处理对传统化学退浆的影响,利用He/O2常压等离子体射流(APPJ)对混合浆料上浆的织物进行预处理,随后在NaHCO3溶液中进行退浆。AFM测试结果表明,经等离子体处理后,上浆织物表而变得粗糙。未处理样品和等离子体处理15s、45s后,表面平均粗糙度分别为2.2,8.9和26.8nm,粗糙度均方根分别为2.8,11.4和33.1nm。XPS测试表明,经等离子体处理后,上浆织物表面的化学成分发生了显著变化。样品表面的氧含量显著增加,说明大量的含氧活性基团引入到表面,增加了浆料的亲水性。退浆率结果显示,等离子体预处理大大的提高了NaHCO3退浆的效率.随着等离子体处理时间的增加,碱退浆率显著增加。对于未经等离子体处理的样品,碱退浆率仅为77%,而经等离子体处理45s后,随后进行相同工艺的碱退浆,退浆率可以达到95%以上。同时,等离子体预处理可以在一定程度上减小碱退浆的温度,并显著地缩短碱退退浆的时间。
为了研究等离子体预处理对超声波退浆的影响,利用等离子体对混合浆料上浆的织物进行预处理,随后在超声波环境下进行退浆。随着等离子体处理时间的延长,上浆织物表面的粗糙度增加,并且有大量的亲水极性基因引入到织物表面。退浆试验结果表明,仅仅使用超声波,退浆效果基本没有。但仅通过等离子体处理就可在80℃下获得大约95%退浆率。然而,等离子体与超声波联合退浆,可在较低的温度下实现较高的退浆率。经等离子体处理50s后,再在60℃下经20分钟超声波退浆,退浆率可达到98%以上,并且随着等离子体处理时间的增加,超声波退浆率增加。此外,与仅通过等离子体退浆的试样相比,等离子体和超声波联合退浆的试样的芯吸高度分别增加了9.7%,12.9%,15.1%和10.1%。芯吸高度的增加表明等离子体和超声波联合处理能够有效去除棉织物表面的绝大部分浆料,提高了退浆效率。
在研究等离子体预处理对传统去除磷酸酯淀粉和聚乙烯醇(PVA)混合浆料后,本论文又研究了等离子体处理对NaHCO3去除涤纶织物上聚丙烯酸酯浆料的影响。AFM测试结果表明,随着等离子体处理时间的增加,聚丙烯酸酯浆料表面粗糙度显著增加。对于未经处理、35s处理和50s处理得薄膜,表面粗糙度(Ra)值分别为0.93,9.15和15.97nm。同时,浆料表面的氧含量也得到了大大提高,大量的亲水性基团C-O-H、 O=C-O在浆料表面生产,提高了聚丙烯酸酯浆料的亲水性。失重率结果显示,随着等离子体处理时间的延长,失重率增加。但当处理时间超过50s后,失重率的增量放缓。退浆结果显示,随着氦/氧气等离子体处理时间的增加,湿退浆的退浆率有了显著提高。经过65s的等离子体预处理,随后在经过5min的湿处理,退浆率可以达到99%以上。然面,在相同的湿退浆条件下,对于没有经过预处理的面料,退浆率仅有28%左右。此外,退浆率随着退浆温度和时间的增加面增大。等离子体处理不能明显的降低湿退浆温度,但能显著地减少退浆时间。
In the textile industry, many starches and modified starches, polyvinyl alcohol (PVA) and polyacrylate are widely used as sizing agent for fabric. But sized fabrics have to be desized to meet the subsequent processing (dyeing, printing and finishing). In conventional desizing processes, the sized fabrics are washed with hot water and NaOH to remove size agents. Because of the high pH values in this method, the treatment should be followed by intensive rinsing and neutralizing, which means that large amount of water and energy is also consumed. The status shows that about900millions tons of waste water is used every year in textile industry. Moreover, the aggressive scouring treatment conditions frequently damage the fiber. Obviously, this desizing process is unable to meet the requirement of environmental protection and quite adverse to the sustainable development of textile industry. Therefore, in order to deal with the problems, the processing route of desizing and finishing needs to be improved.
Compared with the conventional chemical processes, plasma treatment does not require the use of water and chemicals, resulting in the drastic reduction in pollutants and a corresponding cost reduction for effluent treatment. Plasma treatment is an environmentally friendly technique without affecting the bulk properties of textiles. As a high-efficiency surface modification technology, more and more researchers pay close attention to the application of plasma treatment in the pre-treatment and finishing of textiles. If plasma technology can be applied in textile desizing process, both chemical agents and wastewater will be significantly reduced. Meanwhile, the consumption of energy and water can be greatly decreased. Therefore, it has great environmental and economical benefits.
However, previously study mostly focused on the treatment of low-pressure plasma to textiles. The low-pressure plasma involves a vacuum system and thus may not be continuous processes. Compared with low-pressure plasma, the atmospheric pressure plasma treatments do not require a vacuum system and therefore can be applied on-line for substrates. And it is not doubtable that the electron temperature is much lower in the atmospheric pressure plasma in comparison to the typical low-pressure reactor, therefore they are particularly suited to apply to textile processing because most textile materials are heat sensitive polymers. In addition, it is a versatile technique, where a large variety of chemically active functional groups can be incorporated into the textile surface. The possible aims of this are improved wettability, adhesion of coatings, printability, induced hydro-and/or oleophobic properties, changing physical and/or electrical properties, cleaning or disinfection of fiber surfaces etc. But, there is difference in interaction of plasma and textiles between low and atmospheric pressure. At atmospheric pressure, especially for atmospheric pressure plasma jet, plasma is generated in noddle and ejects to form plasma jet, then reaches onto the surface of the materials. So, the plasma treatment parameters, such as the distance between noddle and material, treatemt time, component and flow velocity of gas, etc., influence the plasma treatment effect. Moreover, because the atmospheric pressure plasma treatment is in atmosphere, the substrate material may absorb significant amount of water. The existence of water molecules can lead to a more complicated interaction between active species in plasma and substrate surface
The previously study of plasma desizing mostly focused on the removal of the single size agent (such as PVA). and up to now, there are few report about plasma desizing blended size and combination of plasma and traditional desizing method. Therefore, the objective of this study is to investigate the influence of plasma-wet treatment on desizing of sized fabrics with blended size agent by atmospheric pressure plasma jet (APPJ), andi studied the influence of plasma treatment parameters and moisture content in fabric on plasma etching and surface morphological of size film. Morphological and chemical changes on the fabric surface are characterized by Scanning Electron Microscope (SEM), Atomic force Microscope (AFM) and X-ray Photoelectron Spectra (XPS), respectively. My measurement of weight loss and percent desizing rate lo discuss and analyse the inlluence of plasma treatment on plasma directly removal of size and on subsequence wet desizing effect. The wettability of desized fabric is characterized by wicking height.
Firstly, the inlluence of different processing parameters (treatment lime, jet to substrate distance and gas flow rale) on the etching effect and surface morphology of blended size film of phosphate starch and PVA by He/O2atmospheric pressure plasma jet (APPJ). The results show that as the increase of treatment time and O2flow rate, the weight loss, surface roughness and surface area of size film increase. But, after treatment time is over45s, the increment of weight loss decreases. Moreover, the weight loss, surface roughness and surface area of size film increase firstly and then decrease as the jet to substrate distance increases. When the distance is over6mm, there almost are no treatment effect on the surface, but when the distance is2mm, the best treatment effect can be observed. The research results also show that plasma treatment can introduce more oxygen-contained active groups onto the size film surface, which improve the hydrophilcity of blended size.
Secondly, to investigate the relationship between the absorbed moisture and plasma treatment effect, atmospheric pressure plasma jet (APPJ) is used to treat the blended size film of phosphate starch and PVA with moisture regain (MR) of3.2%、10.5%and79.2%corresponding to10%、65%and97%relative humidity (RH), respectively. Atomic Force Microscope (AFM) result shows that after plasma treatment, the surface roughness of all three group samples obviously increase. As the increase of absorbed moisture, the surface roughness increase firstly and then decrease. When increase the RH from10%to65%. the surface roughness increase from16.01nm to16.62nm. But further increase RH to97%. the roughness is only13.59nm. The weight loss result indicates that the weight loss increase as the increase of absorbed moisture. But compared with surface roughness, there is no direct relation between weight loss and roughness under certain conditions, that is higher etching rate may be not result in rougher surface after plasma treatment. The desizing results show that as the increase of plasma treatment, the percent desizing rale (PDR) increase for the all samples. And the PDR decrease as the increase of absorbed moisture of blended size. When plasma treatment is under10%RH, the PDR is the biggest, about96%. But when RH is97%. the PDR is only about90%.
To investigate the influence of plasma treatment on conventional wet desizing. the sized fabrics are treated by He/O2atmospheric pressure plasma jet (APPJ). subsequently the treated fabrics are desized by NaHCO3. AFM analysis shows that the surfaces of sized fabrics become rougher after plasma treatment. The Ra values were2.2.8.9and26.8nm and the Rms values were2.8,11.4and33.1nm for untreated, the plasma treated for15and45s. respectively. XPS analysis indicates that the surface chemical composition of sized fabrics is greatly changed after plasma treatment. Compared to the untreated, the oxygen content increased significantly indicating oxygen containing polar groups introduced onto the surface after He/O2plasma exposure, which improves the hydrophilicity of blended size. The desizing results show that plasma pre-treatment significantly improves the NaHCO3desizing effect. As the increase of plasma treatment time, the percent desizing rate of NaHCO3increases. Only about77%PDR could be reached for the untreated fabrics, whereas more than95%PDR was achieved after45s plasma treatment followed by the same NaHCO3desizing process. Plasma pre-treatment can decrease the NaHCO3desizing temperature to some extent, and significantly shorten NaHCO3desizing time.
To investigate the influence of plasma pre-treatment on ultrasound desizing, the sized fabrics with blended size is treated by APPJ, and subsequently the treated fabric is desized by ultrasound. As the increase of plasma treatment time, the surface of sized fabric becomes rougher, and more oxygen-containing polar groups are introducted onto the surface of fabric. The desizing results show that only ultrasound treatment almost can not remove the size from fabric surface. But, only plasma treatment can observe about95%PDR at80°C. However, the combination of plasma and ultrasound can observe higher PDR at lower desizing temperature. The PDR reached98.3%for the fabrics with50s plasma treatment followed by ultrasound desizing at60°C for20min. And as the increase of plasma treatment time, the PDR of ultrasound treatment increase. Moreover, compared with the samples with plasma treatment only, the relative increase of the capillary height of the fabrics desized by the plasma-ultrasound were9.7%.12.9%.15.1%and10.1%. respectively. The increase of capillary heights indicated that plasma treatment followed by the ultrasound desizing could effectively remove most of the blended size on cotton fabrics
Finally, the relationship between APPJ and NaHCO3removing polyacrylate sixes from PET fabric is also studied. AFM analysis shows that the surfaces became progressively rougher after the plasma treatment. The Ra values are0.93,9.15and15.97nm for the untreated sample, the plasma treated for35and50s. respectively. And compared to the untreated sample, the O/C ratios for all two plasma-treated fabrics increased dramatically with an increase of treated time suggesting that oxidation occurred and a higher level of oxygen-based functional groups (C-O-H, O=C-O)were formed on the surface exposed to He/O2APPJ. The increase of these polar groups is responsible for the higher hydrophibilily of the polyaerylate size. The weight loss result indicates that the weight loss increased with an increase of plasma treatment time. Hlowever, after50s exposure time, the increment of weight losses slow down. The desizing results show that as the helium/oxygen plasma treatment time increase, the PDR has a significant increase after wet desizing. More than99%PDR was achieved after65s plasma treatment followed by a5min wet desizing, whereas only about28%PDR can be reached for the untreated fabrics. Moreover, the PDR of the all samples increases with the increase of wet desizing temperature and time. Meanwhile plasma treatment can not observably decrease desizing temperature but dramaticlly reduce desizing time.
引文
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