Journal of Textile Research ›› 2023, Vol. 44 ›› Issue (09): 223-231.doi: 10.13475/j.fzxb.20220401302

• Comprehensive Review • Previous Articles     Next Articles

Progress in preparation and application of graphene modified silk

HE Kaijun1, SHEN Jiajia2(), LIU Guojin3   

  1. 1. School of Advanced Materials Engineering, Jiaxing Nanhu University, Jiaxing, Zhejiang 314001, China
    2. College of Materials and Textile Engineering, Jiaxing University, Jiaxing, Zhejiang 314001, China
    3. Zhejiang Provincial Key Laboratory of Fiber Materials and Manufacturing Technology, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018, China
  • Received:2022-04-02 Revised:2022-11-09 Online:2023-09-15 Published:2023-10-30

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Abstract:

Significance Fibers and fabrics are the main components of conventional wearable products because of its good flexibility, air permeability and mechanical properties. However, with the rapid development of science and technology and the improvement of people's living standards, the future textiles need to retain the advantages of conventional fibers and fabrics while providing them multi-functional and intelligent characteristics. Compared with other man-made chemical polymer materials, natural biomaterials have the advantages of being environmentally friendly, biodegradable, and sustainable among many others. Natural silk from silkworms has been used in clothing for thousands of years and can be continuously obtained and used in large quantities. Silk is a natural protein fiber with excellent mechanical properties, good flexibility, biocompatibility and biodegradability. Two-dimensional nano-graphene and its derivative materials with excellent thermal conductivity, biocompatibility and mechanical properties were synergistically combined with silk. By optimizing the interaction between silk and graphene materials, the properties and functions of silk can be further enhanced and enriched, and its applications in the field of textile and biomedical flexible wearables can be expanded. This paper reviews the latest research progress in graphene modified silk materials to identify research gaps for research.

Progress Because of the unique natural layered structure of silk and the excellent functionality of graphene material, graphene modified silk materials have been widely favored in the field of intelligent textiles. This paper firstly introduced the preparation methods of graphene modified silk. While retaining the natural structure and properties of silk, it can also endow silk with new functions. There are mainly two methods for attaching graphene and its derivatives uniformly and stably on silk, that is, internal modification and external modification. The internal modification mainly refers to the in vivo uptake of graphene materials by silkworms during their growth, including feeding method and in vivo injection method, and the external modification, also known as surface finishing method, includes dip-rolling coating method, dip coating method, spraying method, dry coating method and layer self-assembly method. The preparation methods of graphene modified silk materials were compared (Tab. 1), and the improvement of silk properties by graphene materials, including mechanical properties, electrical conductivity and multi-functional wearability, was reviewed. In addition, the applications of graphene modified silk in sensors, including respiratory sensor, gas sensor and infrared sensor, were scrutinized and summarized. It is believed that silk materials have great potential in multi-functional and intelligent textiles.

Conclusion and Prospect Graphene modified silk materials have laid a foundation for the development of flexible electronic wearable field in the fields of mechanical properties, electrical conductivity and biological adaptability. However, the low loading of graphene and the weak interfacial bonding force on silk are still yet satisfy the special required functions in some respects, which is the key and difficult point to be solved. The interfacial forces between graphene materials and silk, such as hydrogen bond, Van Der Waals force, and covalent bond, determine the loading capacity and durability of graphene on silk, and then affect the performance of modified silk. The reviewed researches include the assembly method of graphene on silk, the reduction method of graphene oxide, the pH value of solution, the screening of additives and other processes to obtain graphene modified silk materials with stable structure, excellent performance and complete functions. The preparation method of graphene functionalized silk with low cost, high efficiency and environment friendliness, the interface bonding force and working mechanism between graphene materials and silk, and the changes of secondary structure of modified silk are the main perspectives that has drawn research attention, which also determine the application of graphene modified silk materials in various fields. Researches also shows that single functionalization does not satisfy the application of silk in textile and biomedicine, hence it becomes imperative to develop multi-functionalization of graphene silk materials. For example, it is necessary to build a ternary or multivariate functional modification system, introduce environmentally friendly cross-linking additives, biomolecules and other modified materials with different sizes and functions in the process of modification of silk with graphene, increase the load of graphene on modified silk materials and endow it with multi-function, so as to expand its application in the textile and biomedical fields.

Key words: silk, graphene material, modification, graphene modified silk, flexible and wearable

CLC Number: 

  • TS195.5

Tab. 1

Comparison of preparation methods of graphene-modified silk"

方法 优点 缺点
体内注射法 步骤简单,摄入量可控,牢度高,持久性强 操作较难,对家蚕生长有影响,大规模生产难,摄入量低
添食法 简便,持久,低价高效且生态环保,可大批量生产 转化率低且不可控,对家蚕生长有一定影响,摄入量低
浸轧涂层法 方法简便易操作,负载量大 耗材量大,均匀性难把握,与织物结合强度差
浸渍涂层法 方法简便易操作,多次操作可实现高负载量 需整理液多,时间长影响生产效率,牢度差
喷涂法 成本低,操作简单,无组织结构要求,图案可控制 弹性差,均匀性和持久性较差
干法涂层法 表面吸附量高,厚度可调节 透气率差,耐水洗和持久性较弱,手感较差
层层自组装法 表面吸附量高,厚度可控 循环次数多,时间长影响生产效率,手感较差
[1] ZHONG J, LIU X W, WEI D X, et al. Effect of incubation temperature on the self-assembly of regenerated silk fibroin: a study using AFM[J]. International Journal of Biological Macromolecules, 2015, 76:195-202.
doi: 10.1016/j.ijbiomac.2015.02.045 pmid: 25748848
[2] VEPARI C, KAPLAN D L. Silk as a biomaterial[J]. Progress in Polymer Science, 2007, 32(8-9): 991-1007.
doi: 10.1016/j.progpolymsci.2007.05.013 pmid: 19543442
[3] ZHANG Y Q, WANG Y J, WANG H Y, et al. Highly efficient processing of silk fibroin nanoparticle-lasparaginase bioconjugates and their characterization as a drug delivery system[J]. Soft Matter, 2011, 7(20): 9728-9736.
doi: 10.1039/c0sm01332c
[4] KIM K S, ZHAO Y, JANG H, et al. Large-scale pattern growth of graphene films for stretchable transparent electrodes[J]. Nature, 2009, 457(7230): 706-710.
doi: 10.1038/nature07719
[5] BALANDIN A A, GHOSH S, BAO W Z, et al. Superior thermal conductivity of single-layer graphene[J]. Nano Letters, 2008, 8(3): 902-907.
doi: 10.1021/nl0731872 pmid: 18284217
[6] LEE C, WEI X D, KYSAR J W, et al. Measurement of the elastic properties and intrinsic strength of monolayer graphene[J]. Science, 2008, 321 (5887):385-388.
doi: 10.1126/science.1157996 pmid: 18635798
[7] ZHU Y W, MURALI S S, CAI W, et al. Graphene and graphene oxide: synthesis, properties, and applic-ations[J]. Advanced Materials, 2010, 22(46):3906-3924.
doi: 10.1002/adma.v22:35
[8] PENG L, XU Z, LIU Z, et al. An iron-based green approach to 1-h production of single-layer graphene oxide[J]. Nature Communications, 2015. DOI: 10.1038/ncomms6716.
[9] MOLINA J, FEMANDEZ J, INES J C, et al. Electrochemical characterization of reduced graphene oxide-coated polyester fabrics[J]. Electrochimica Acta, 2013, 93: 44-52.
doi: 10.1016/j.electacta.2013.01.071
[10] YE C, REN J, WANG Y L, et al. Design and fabrication of silk templated electronic yarns and applications in multifunctional textiles[J]. Matter, 2019, 1(5): 1411-1425.
doi: 10.1016/j.matt.2019.07.016
[11] WANG Y, GUO J, ZHOU L, et al. Design, fabrication, and function of silk-based nano-materials[J]. Advanced Functional Materials, 2018. DOI: 10.1002/adfm.201805305.
[12] WANG Q, WANG C, ZHANG M, et al. Feeding single-walled carbon nanotubes or graphene to silkworms for reinforced silk fibers[J]. Nano Letters, 2016, 16(10): 6695-6700.
pmid: 27623222
[13] ALTMAN G H, DIAZ F, JAKUBA C, et al. Silk-based biomaterials[J]. Biomaterials, 2003, 24(3): 401-416.
doi: 10.1016/s0142-9612(02)00353-8 pmid: 12423595
[14] ROCKWOOD D N, PREDA R C, YUCEL T, et al. Materials fabrication from bombyx mori silk fibroin[J]. Nature Protocols, 2011, 6(10): 1612-1631.
doi: 10.1038/nprot.2011.379 pmid: 21959241
[15] LING S, LI C, JIN K, et al. Liquid exfoliated natural silk nanofibrils: applications in optical and electrical devices[J]. Advanced Materials, 2016, 28(35):7783-7790.
doi: 10.1002/adma.v28.35
[16] YUE X, FENG Z, WU H, et al. A novel route to prepare dry-spun silk fibers from CaCl2-formic acid solution[J]. Materials Letters, 2014, 128:175-178.
doi: 10.1016/j.matlet.2014.04.116
[17] ZHENG K, ZHONG J, QI Z, et al. Isolation of silk mesostructures for electronic and environmental applications[J]. Advanced Functional Materials, 2018. DOI: 10.1002/adfm.201806380.
[18] TANSIL N C, KOH L D, HAN M Y. Functional silk: colored and luminescent[J]. Advanced Materials, 2012, 24:1388-1397.
doi: 10.1002/adma.v24.11
[19] LU Z, MAO C, MENG M, et al. Fabrication of CeO2 nanoparticlemodified silk for UV protection and antibacterial applications[J]. Journal of Colloid and Interface Science, 2014, 435:8-14.
doi: 10.1016/j.jcis.2014.08.015
[20] WANG X, GAO W, XU S, et al. Luminescent fibers: in situ synthesis of silver nanoclusters on silk via ultraviolet light-induced reduction and their antibacterial activity[J]. Chemial Engineering Journal, 2012, 210:585-589.
[21] ZHANG P, LAN J, WANG Y, et al. Luminescent golden silk and fabric through in situ chemically coating pristine-silk with gold nanoclusters[J]. Biomaterials, 2015, 36:26-32.
doi: 10.1016/j.biomaterials.2014.08.026 pmid: 25308521
[22] FERNANDES J, NICODEMO D, OLIVEIRA J E, et al. Enhanced silk performance by enriching the silkworm diet with bordeaux mixture[J]. Journal of Materials Science, 2017, 52: 2684-2693.
doi: 10.1007/s10853-016-0559-3
[23] WU G H, SONG P, ZHANG D Y, et al. Robust composite silk fibers pulled out of silkworms directly fed with nanoparticles[J]. International Journal of Biological Macromolecules, 2017, 104: 533-538.
doi: S0141-8130(16)32887-2 pmid: 28625835
[24] DREYER D R, PARK S, BIELAWSKI C W, et al. The chemistry of graphene oxide[J]. Chemical Society Reviews, 2010, 39: 228-240.
doi: 10.1039/b917103g pmid: 20023850
[25] LU Z, MAO C, ZHANG H. Highly conductive graphene-coated silk fabricated via a repeated coating-reduction approach[J]. Journal of Materials Chemistry C, 2015, 3(17): 4265-4268.
doi: 10.1039/C5TC00917K
[26] CAO J L, WANG C X. Multifunctional surface modification of silk fabric via graphene oxide repeatedly coating and chemical reduction method[J]. Applied Surface Science, 2017, 405(1): 380-388.
doi: 10.1016/j.apsusc.2017.02.017
[27] ZHANG X, LICON A L, HARRIS T I, et al. Silkworms with spider silklike fibers using synthetic silkworm chow containing calcium lignosulfonate, carbon nanotubes, and graphene[J]. ACS Omega, 2019, 4(3): 4832-4838.
doi: 10.1021/acsomega.8b03566 pmid: 31459667
[28] CHENG L, ZHAO H P, HUANG H M, et al. Quantum dots-reinforced luminescent silkworm silk with superior mechanical properties and highly stable fluorescence[J]. Journal of Materials Science, 2019, 54(13): 9945-9957.
doi: 10.1007/s10853-019-03469-w
[29] ZHOU B, WANG H, ZHOU H, et al. Natural flat cocoon materials constructed by eri silkworm with high strength and excellent anti-ultraviolet performance[J]. Journal of Engineered Fibers and Fabrics, 2020. DOI: 10.1177/1558925020978652.
[30] MA L, AKURUGU M A, ANDOH V, et al. Intrinsically reinforced silks obtained by incorporation of graphene quantum dots into silkworms[J]. Science China Materials, 2019, 62(2): 245-255.
doi: 10.1007/s40843-018-9307-7
[31] LU W, LU C, LI Y, et al. Green fabrication of porous silk fibroin/graphene oxide hybrid scaffolds for bone tissue engineering[J]. RSC Advances, 2015, 5(96):78660-78668.
doi: 10.1039/C5RA12173F
[32] CAO C, LIN Z, CHENG Q, et al. Strong reduced graphene oxide coated bombyx mori silk[J]. Advanced Functional Materials, 2021. DOI: 10.1002/adfm.202102923.
[33] SONG J C, XU S J, CHEN T, et al. Preparation of graphene oxide-coated silk fibers through HBPAA [a molecular glue]-induced layer-by-layer self-assembly[J]. Journal of the Iranian Chemical Society, 2018, 15(1): 101-109.
doi: 10.1007/s13738-017-1213-y
[34] JI Y M, CHEN G Q, XING T L. Rational design and preparation of flame retardant silk fabrics coated with reduced graphene oxide[J]. Applied Surface Science, 2019, 474: 203-210.
doi: 10.1016/j.apsusc.2018.03.120
[35] LIU Z L, LI Z, CHENG L, et al. Reduced graphene oxide coated silk fabrics with conductive property for wearable electronic textiles application[J]. Advanced Electronic Materials, 2019. DOI: 10.1002/aelm.201800648.
[36] SONG X, LIU X T, PENG Y X, et al. A graphene-coated silk-spandex fabric strain sensor for human movement monitoring and recognition[J]. Nanotechnology, 2021. DOI: 10.1088/1361-6528/abe788.
[37] BHATTACHARJEE S, MACINTYRE C R, BAHL P, et al. Reduced graphene oxide and nanoparticles incorporated durable electroconductive silk fabrics[J]. Advanced Materials Interfaces, 2020. DOI: 10.1002/admi.202000814.
[38] JUNG W T, JANG H S, JEON J W, et al. Effect of oxygen functional groups in reduced graphene oxide coated silk electronic textiles for enhancement of NO2 gas-sensing performance[J]. ACS Omega, 2021, 6: 27080-27088.
doi: 10.1021/acsomega.1c03658
[39] LI B T, XIAO G, LIU F, et al. A flexible humidity sensor based on silk fabrics for human respiration monitoring[J]. Journal of Materials Chemistry C, 2018, 6(16): 4549-4554.
doi: 10.1039/C8TC00238J
[40] JI Y M, LI Y Z, CHEN G Q, et al. Fire-resistant and highly electrically conductive silk fabrics fabricated with reduced graphene oxide via dry-coating[J]. Materials & Design, 2017, 133: 528-535.
[41] SAHITO I A, SUN K C, ARBAB A A, et al. Integrating high electrical conductivity and photocatalytic activity in cotton fabric by cationizing for enriched coating of negatively charged graphene oxide[J]. Carbohydrate Polymers, 2015, 130: 299-306.
doi: 10.1016/j.carbpol.2015.05.010 pmid: 26076630
[42] MOLINAAB J, FERNANDEZ J, FERNANDES M, et al. Plasma treatment of polyester fabrics to increase the adhesion of reduced graphene oxide[J]. Synthetic Metals, 2015, 202: 110-122.
doi: 10.1016/j.synthmet.2015.01.023
[43] CAO J L, WANG C X. Highly conductive and flexible silk fabric via electrostatic self assemble between reduced graphene oxide and polyaniline[J]. Organic Electronics, 2018, 55: 26-34.
doi: 10.1016/j.orgel.2017.12.016
[44] QU J, DAI M, YE W, et al. Study on the effect of graphene oxide (GO) feeding on silk properties based on segmented precise measurement[J]. Journal of the Mechanical Behavior of Biomedical Materials, 2021. DOI: 10.1016/j.jmbbm.2020.104147.
[45] WANG S, NING H M, HU N, et al. Environmentally-friendly and multifunctional graphene-silk fabric strain sensor for human-motion detection[J]. Advanced Materials Interfaces, 2019. DOI: 10.1002/admi.201901507.
[46] STOPPA M, CHIOLERIO A. Wearable electronics and smart textiles: a critical review[J]. Sensors, 2014, 14(7): 11957-11992.
doi: 10.3390/s140711957 pmid: 25004153
[47] QIU Q, ZHU M, LI Z, et al. Highly flexible, breathable, tailorable and washable power generation fabrics for wearable electronics[J]. Nano Energy, 2019, 58: 750-758.
doi: 10.1016/j.nanoen.2019.02.010
[48] MOLINA J, FERNANDEZ J, INES J C, et al. Electrochemical characterization of reduced graphene oxide-coated polyester fabrics[J]. Electrochimica Acta, 2013, 93: 44-52.
doi: 10.1016/j.electacta.2013.01.071
[49] DIN M I, REHAN R. Synthesis, characterization, and applications of copper nanoparticles[J]. Analytical Letters, 2017, 50(1): 50-62.
doi: 10.1080/00032719.2016.1172081
[50] QU L, TIAN M, HU X, et al. Functionalization of cotton fabric at low graphene nanoplate content for ultrastrong ultraviolet blocking[J]. Carbon, 2014, 80: 565-574.
doi: 10.1016/j.carbon.2014.08.097
[51] HU W B, PENG C, LUO W J, et al. Graphene based antibacterial paper[J]. ACS Nano, 2010, 4: 4317-4323.
doi: 10.1021/nn101097v
[52] TU T, LÜ M, XIU P, et al. Destructive extraction of phospholipids from escherichia coli membranes by graphene nanosheets[J]. Nature Nanotechnology, 2013, 8: 594-601.
doi: 10.1038/nnano.2013.125 pmid: 23832191
[53] WANG S D, WANG K, MA Q, et al. Fabrication of the multifunctional durable silk fabric with synthesized graphene oxide nanosheets[J]. Materials Today Communi cations, 2020. DOI: 10.1016/j.mtcomm.2020.100893.
[54] BORINI S, WHITE R, WEI D, et al. Ultrafast graphene oxide humidity sensors[J]. ACS Nano, 2013, 7(12): 11166-11173.
doi: 10.1021/nn404889b pmid: 24206232
[55] SONG Y, LIN Z, KONG L, et al. Meso-functionalization of silk fibroin by upconversion fluorescence and near infrared in vivo biosensing[J]. Advanced Functional Materials, 2017. DOI: 10.1002/adfm.201700628.
[56] MIN K, KIM S, KIM C G, et al. Colored and fluorescent nanofibrous silk as a physically transient chemosensor and vitamin deliverer[J]. Scientific Reports, 2017. DOI: 10.1038/s41598-017-05842-8.
[57] YAO Y, CHEN X D, GUO H H, et al. Humidity sensing behaviors of graphene oxide-silicon bi-layer flexible structure[J]. Sensors & Actuators: B. Chemical, 2012, 161(1): 1053-1058.
[58] FIRAT G, ALAR A, JULIA R, et al. Paper-based electrical respiration sensor[J]. Angewandte Chemie International Edition, 2016, 55(19): 5727-5732.
doi: 10.1002/anie.v55.19
[59] KAMPA M, CASTANAS E. Human health effects of air pollution[J]. Environmental Pollution, 2008, 151:362-367.
doi: 10.1016/j.envpol.2007.06.012 pmid: 17646040
[60] VARGHESE S S, LONKAR S, SINGH K K, et al. Recent advances in graphene based gas sensors[J]. Sensors & Actuators: B. Chemical, 2015, 218: 160-183.
[61] CHOI Y R, YOON Y G, CHOI K S, et al. Role of oxygen functional groups in graphene oxide for reversible room-temperature NO2 sensing[J]. Carbon, 2015, 91: 178-187.
doi: 10.1016/j.carbon.2015.04.082
[62] SCHEDIN F, GEIM A K, MOROZOV S V, et al. Detection of individual gas molecules adsorbed on graphene[J]. Nature Materials, 2007, 6: 652-655.
doi: 10.1038/nmat1967 pmid: 17660825
[63] SHI L H, HUANG Y, GAO L, et al. Application of graphene in coating silk fibril for tunable infrared absorption[J]. Journal of Electronic Materials, 2021, 50(2): 592-597.
doi: 10.1007/s11664-020-08589-7
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