Universidade do Minho Escola de Engenharia NGUYEN KHANH VU Application of plasma treatment to textile substrates in order to enhance the adsorption of nanoparticles Master in Advanced Textiles Multifunctional Textiles Trabalho efectuado sob a orientação do Professor Doutor António Pedro Garcia de Valadares Souto July 2012 Application of plasma treatment to textile substrates in order to enhance the adsorption of nanoparticles “Study, study more, study forever” Vladimir Ilyich Lenin iii Application of plasma treatment to textile substrates in order to enhance the adsorption of nanoparticles ACKNOWLEDGEMENTS In order to successfully fulfill my thesis, I had a lot of support and encouragements from people around me. I would like, hence, to express my gratitude to all those who contributed in certain ways to the completion of my work. First, I want to show my deep gracefulness to Professor Pedro Souto, who gave me a lot of invaluable knowledge as well as his orientations for the first fundamental steps of my career in science. It is a big honor to be accepted as a master student under your supervision.
Second, I would like to thank Mr. It is a sudden luck that I am able to work aside him, who has spent his precious time explaining doubts and wonderings of mine during the preparation of my thesis. Furthermore, I want also to say thank to Professor Ana Rocha, my coordinator at University of Minho over the past two years, who also plays a very important role of my study during my course Master in High– tech. And for all Staff, Professors, I hope they can understand my appreciation of their support, help and friendly environment they created for me.
Besides Professors, Counselors, everyone does have friends. In my case, I want to send my love to Fernando, Fernanda, Marta, Angela, Juliana, Sandra, Heriberto and many others those I can’t name all, who shared their experiences with me during lab work, lunches. Those times were very fantastic for me. Some people I am not allowed to forget are Staff from EM–EuroAsia 2010–2012 project, whom I just can narrate here as representatives, they are Ms.
Mette Svensson from Boras University (the Host of this project), Ms. Andriana Carvalho from University of Minho and Mr. Nguyen Hoang Nam from Ho Chi Minh City University of Technology. Thanks to their kindness, I was able to implement my dream of studying and researching.
Moreover, I want to say thank to all of my friends who made my experiences in Portugal become unforgettable in my life time iv Application of plasma treatment to textile substrates in order to enhance the adsorption of nanoparticles Finally, there are people whom anyone must miss are his/her family members. I just don’t know phrases or sentences which I can use to depict my profound emotions to them. I want to say thousands of thanks to my own parents (bố Minh, mẹ Trúc), my parents–in–law (ba Khánh, mẹ Tuyết), my aunts (dì Nguyệt, dì Thủy, dì Tư Thủy), my uncles (bác Ba, bác Tư Tuyết), my sister (bé Ngọc) and my cousins (Bu, Tí, Khoa). These people are my motivations, my hope that encourages me not only my study here in Portugal but for the rest of my life.
Last but not least, the most important person, my dearest wife, Phan Xuân Khánh Yên, who sacrificed here career so as she can come to stay with me, take care of me when I study in Guimarães. She shared with me both sadness and happiness. She is one of the most paramount key factors affecting my thesis. I want to show you my endless love to her and our going–to– be–born kid in her.
v Application of plasma treatment to textile substrates in order to enhance the adsorption of nanoparticles This master thesis has been finished thanks to the sponsorship of an Erasmus project called EM–EuroAsia which is under the auspices of The European Commission. vi Application of plasma treatment to textile substrates in order to enhance the adsorption of nanoparticles RESUMO A tecnologia plasmática de dupla barreira dieléctrica (DBD) pertence à classe de plasma a frio de baixa frequência utilizado a pressão atmosférica. Deve ser alimentado por uma corrente alternada e accionado por uma energia de alta tensão que pode variar entre 1–100kHz. Este método é especialmente utilizado em aplicações com sistemas roll–to–roll que são termicamente sensíveis, por exemplo, películas, folhas de papel para impressão gráfica, membranas poliméricas e materiais têxteis.
Para além destes produtos, a tecnologia DBD pode ser aplicada a outros tipos de materiais, tais como madeira, cabos isoladores ou até mesmo em unhas humanas. A aplicação mais comum em substratos têxteis tem como objetivo melhorar a molhabilidade e aumentar determinados grupos polares na superfície do material. No entanto, outras diversas propriedades podem também ser modificadas, nomeadamente; a energia de superfície, o coeficiente de atrito, o comportamento anti–estático, dentre outros. Desta forma, a modificação via descarga DBD é a técnica mais aplicada quando se pretende alterar superficialmente diversos tipos de materiais.
Por ser tratar de uma tecnologia de facil implementação industrial, este equipamento tem um grande potencial para ser adaptado a muitas indústrias, incluindo a têxtil. Na última década, a utilização de nanopartículas tornou–se uma das áreas científicas mais atraentes a serem exploradas. No entanto, a aplicação de nanopartículas em substratos têxteis possui a limitação da aderência ao substrato, com solidezes à lavagem ou fricção mais baixas do que o desejado. Portanto, a melhoria desta ligação interfacial é uma necessidade presente.
Este trabalho utilizou um protótipo semi–industrial de plasma DBD, com o intuito de modificar superficialmente as propriedades físico–químicas de um tecido de poliamida 66, com a finalidade de melhorar a adsorção e adesão de nanopartículas de prata. Para estudar as modificacões superficiais do substrato foram utilizadas as seguintes técnicas de caracterização: ângulo de contato, microscopia electrónica de varrimento (SEM), espectroscopia fotoeletronica de raios–X (XPS) e a espectroscopia de energia dispersiva de raios X (EDX). Os resultados mostraram que a quantidade de nanopartículas de prata adsorvidas teve um aumento significativo no tecido de poliamida previamente tratado com plasma. vii Application of plasma treatment to textile substrates in order to enhance the adsorption of nanoparticles ABSTRACT Plasma Dielectric Barrier Discharge (DBD) technology belongs to the class of cold plasma with low frequency used at atmospheric pressure.
It must be powered by an A. current and driven by a high voltage power running at 1–100 kHz frequency. This approach is specially used on applications with roll– to–roll systems which are thermally sensitive, for instance, foils, photo–graphic print paper, polymeric membranes and textiles. Besides those products, nevertheless, the DBD technology can be also applied to some various materials such as, wood, insulated cable or even to human nails (fingers’ or toes’).
The most common application of textile is to enhance the wettability and polar groups on the material surface. However, there are more properties which can also be modified as surface energy, friction coefficient, and antistatic behaviour, among others. Thus, the DBD plasma modification is the most applied technique when it is intended to modify several types of materials. Because this technology is an easy industrial implementation, this device has great potential to be adapted to many industries, including textiles.
In the last decade, the use of nanoparticles has become one of the most attractive scientific areas to be explored. However, the application of nanoparticles on textile substrates is limited due to its adherence to the substrate with the washing or rubbing fastness than expected. Therefore, the enhancement of interfacial bonding is a present necessity. This study used a semi–industrial DBD plasma prototype to modify the surface of physic–chemical properties of polyamide 66, in order to improve the adherence and adsorption of silver nanoparticles.
To study surface modifications of the substrate, several techniques were used namely, contact angle measurement, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDX). The results showed that the amount of adsorbed silver nanoparticles had a significant increase in polyamide fabric pre–treated with DBD plasma. viii Application of plasma treatment to textile substrates in order to enhance the adsorption of nanoparticles INDEX CONTENT Acknowledgement. xii List of figures.
xiii List of tables. xv CHAPTER 1 – INTRODUCTION. 7 CHAPTER 2 – STATE OF ART. CHEMICAL STRUCTURE AND SYNTHETIC PROCEDURE.
PHYSICAL AND CHEMICAL PROPERTIES. APPLICATIONS OF POLYAMIDE. NANOPARTICLES AND APPLICATIONS. WHAT IS PLASMA?.
PLASMA – SURFACE COLLISION. ATMOSPHERIC PRESSURE PLASMA. TYPICAL APPLICATIONS OF PLASMA TECHNOLOGIES IN TEXTILE AREA. 31 ix Application of plasma treatment to textile substrates in order to enhance the adsorption of nanoparticles INDEX CHAPTER 3 – EXPERIMENTAL PROCEDURE.
DYNAMIC LIGHT SCATTERING. ZETA POTENTIAL MEASUREMENT. CHEMICAL COMPOSITION ANALYSIS. 43 CHAPTER 4 – RESULTS AND DISCUSSIONS.
EDS AND XPS. SCANNING ELECTRON MICROSCOPY (SEM). SILVER NANOPARTICLES CHARACTERIZATION. UV–VIS ABSORPTION SPECTRA.
DYNAMIC LIGHT SCATTERING. 54 x Application of plasma treatment to textile substrates in order to enhance the adsorption of nanoparticles INDEX 4. X–RAY PHOTOELECTRON SCANNING (XPS). 61 CHAPTER 5 – CONCLUSIONS AND FUTURE WORK.
65 xi Application of plasma treatment to textile substrates in order to enhance the adsorption of nanoparticles INDEX ABBREVIATIONS AgNPs Silver nanoparticles APPJ Atmospheric Pressure Plasma Jet At(%) Atomic percentage AuNPs Gold nanoparticles CNTs Carbon nanotubes DBD Dielectric Barrier Discharge DC Direct Current DLS Dynamic Light Scattering EDX/EDS Energy Dispersive X–ray Spectroscopy FTC Federal Trade Commission ILSS inter–laminar shear strength LTCC Low–temperature Co–fired Ceramic PAN Polyacrylonitrile PDI Polydispersity Index SEM Scanning Electron Microscopy STEM Scanning Transmission Electron Microscopy Tg Glass Transition Temperature UV Ultra Violet UV–vis Ultra violet–visible XPS X–ray Photoelectron Spectroscopy xii Application of plasma treatment to textile substrates in order to enhance the adsorption of nanoparticles INDEX LIST OF FIGURES Figure 1.1 – General characterization of plasma techniques 2 Figure 1.2 – Nanocoating, an example of nanofinishing techniques 2 Figure 1.3 – Examples of yarn–to–fabric preforms 4 Figure 2.1 – Several examples of polyamide fibers 10 Figure 2.2 – General production line of polyamide fiber 13 Figure 2.3 – Synthetic fiber–reinforced concrete 15 Figure 2.4 – Sail cloth made of polyamide.5 – Carbon nanotubes structures 17 Figure 2.6 – Applications of carbon nanotubes 18 Figure 2.7 – Scale of things 19 Figure 2.8 – Schematic representation of the bottom–up and top–down approaches for the synthesis of nanomaterials 20 Figure 2.9 – SEM photo of cotton fiber impregnated with AgNPs for antimicrobial property 22 Figure 2.10 – SEM photo of super–hydrophobic textile material created using nanotechnology 24 Figure 2.11 – UV transmittance characteristics of textile materials 25 Figure 2.12 – Lotus Effect® removing dirt particles from super–hydrophobic surface 26 Figure 2.13 – Advantages of plasma treatment over traditional wet chemistry 27 Figure 2.14 – Important collisions between plasma and surfaces 29 Figure 2.15 – Three major types of atmospheric plasma technology 30 Figure 2.16 – Dielectric barrier discharge (DBD) plasma 30 Figure 2.17 – Untreated fiber (left) and plasma treated fiber (right) for the improving pilling property of woollen knitted fabric 32 Figure 2.18 – Wettability of untreated grey cotton fabric (left) and plasma treated grey cotton fabric 33 Figure 2.19 – Exhaustion of Sirius dyes (Orange, Violet, and Blue), in “control” samples and after DBD plasma treatment 34 xiii Application of plasma treatment to textile substrates in order to enhance the adsorption of nanoparticles INDEX Figure 2.20 – Images of polyester fabrics which were taken by DZ3–video focus–exchanged microscope at 75 multiple after inkjet printing with pigment inks 35 Figure 2.21 – Adhesive joint strength of as received titanium and surface modified titanium 37 Figure 3.1 – Semi–industrial prototype of the plasma machine Softal [Pat. PCT/PT 2004/ 000008(2004)] 39 Figure 3.2 – The aligned polyamide 66 samples in covered boxes for silver nanoparticles imbue corresponding with each type of silver nanoparticles 40 Figure 3.1 – Dynamic contact angle 46 Figure 4.