Effects of polymeric dispersants and surfactants on the dispersing stability and high‐speed‐jetting properties of aqueous‐pigment‐based ink‐jet inks

Good jetting performance and pigment‐dispersing stability are necessary for pigment‐based ink‐jet inks. This study investigates how the chemical structures of the polymeric dispersants affect the pigment‐dispersing stability and jetting performance of ink‐jet inks. A series of polymeric dispersants containing styrene (hydrophobic unit) and acrylic acid (hydrophilic unit) with different ratios have been synthesized and used to disperse different pigments. Because 3000–12,000 ink drops can be expelled from the nozzle of a thermal bubble‐type ink‐jet printer within 1 s, the jetting behavior is related to the rheology variation of a dilute solution under a high shear. An in situ drop formation system has been used to study the high‐shear‐rate rheology (dynamic surface tension and dynamic viscosity) of a solution with a viscosity lower than 3 cps, which no commercial rheometer can measure. Excellent ink‐jet inks can only be produced by the combination of pigments, dispersants, and surfactants with appropriate hydrophilicity. Moreover, the correlation of the pigment surface properties, the chemical structures of the polymeric dispersants, and ink formulation is discussed. The effects of the surfactants and firing conditions on the jetting behavior of the ink‐jet ink are also examined. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1909–1920, 2003     

Ink‐Jet Printing of Metallic Nanoparticles and Microemulsions

Summary: Two types of ink‐jet inks are presented: ink containing an aqueous dispersion of silver nanoparticles and an oil‐in‐water microemulsion‐based ink. The metallic ink contains nanoparticles of silver, which are formed in the presence of an ionic polymeric stabilizer. Sintering of the printed image obtained with the use of such silver‐based inks at temperatures as low as 300 °C results in formation of patterns possessing noticeable conductivity. The microemulsion inks are based on a thermodynamically stable microemulsion, in which the dispersed oil phase is a volatile solvent containing a water‐insoluble colorant. After contact of the jetted ink droplets with a substrate, nanodroplets of the microemulsion are converted into nanoparticles of the solubilized colorant. In some cases, it was found that the evaporation of microemulsion ink droplets leads to formation of rings composed of ordered nanoparticles.

Scheme of ink‐jet printing of an oil‐in‐water microemulsion followed by conversion of the nanodroplets into nanoparticles, caused by quick evaporation of the solvent within the microemulsion droplets. Therefore, the ink behaves as a dye‐based ink prior to printing, but after printing it behaves like a pigment‐based ink.     

MODs vs. NPs: Vying for the Future of Printed Electronics

This Minireview compares two distinct ink types, namely metal-organic decomposition (MOD) and nanoparticle (NP) formulations, for use in the printing of some of the most conductive elements: silver, copper and aluminium. Printing of highly conductive features has found purpose across a broad array of electronics and as processing times and temperatures reduce, the avenues of application expand to low-cost flexible substrates, materials for wearable devices and beyond. Printing techniques such as screen, aerosol jet and inkjet printing are scalable, solution-based processes that historically have employed NP formulations to achieve low resistivity coatings printed at high resolution. Since the turn of the century, the rise in MOD inks has vastly extended the range of potentially applicable compounds that can be printed, whilst simultaneously addressing shelf life and sintering issues. A brief introduction to the field and requirements of an ink will be presented followed by a detailed discussion of a wide array of synthetic routes to both MOD and NP inks. Unindustrialized materials will be discussed, with the challenges and outlook considered for the market leaders: silver and copper, in comparison with the emerging field of aluminium inks.     

Biosurface engineering through ink jet printing

The feasibility of thermal ink jet printing as a robust process for biosurface engineering was demonstrated. The strategy investigated was to reconstruct a commercial printer and take advantage of its colour management interface. High printing resolution was achieved by formulating bio-inks of viscosity and surface tension similar to those of commercial inks. Protein and enzyme denaturation during thermal ink jet printing was shown to be insignificant. This is because the time spent by the biomolecules in the heating zone of the printer is negligible; in addition, the air and substrate of high heat capacity absorb any residual heat from the droplet.Gradients of trophic/tropic factors can serve as driving force for cell growth or migration for tissue regeneration. Concentration gradients of proteins were printed on scaffolds to show the capability of ink jet printing. The printed proteins did not desorb upon prolonged immersion in aqueous solutions, thus allowing printed scaffold to be used under in vitro and in vivo conditions. Our group portrait was ink jet printed with a protein on paper, illustrating that complex biopatterns can be printed on large area. Finally, patterns of enzymes were ink jet printed within the detection and reaction zones of a paper diagnostic.     

Scalable Preparation of Photochromic Composite Foils with Excellent Reversibility for Light Printing

Photochromic inks for repeatable light‐printed media have attracted increasing attention owing to the fact that they may be widely applied to reduce the consumption of papers and plastics and conserve the environment. Therefore, it is of practical significance to develop convenient photochromic inks with a low cost and on a large scale. In this study, a simple one‐step hydrothermal route was used to prepare tungsten trioxide (WO₃) nanoparticles, which were further used to make photochromic inks and transparent photochromic films. The obtained transparent photochromic film could rapidly respond to UV light within tens of seconds, then return to its initial state, with different recovery times at different temperatures, and also exhibit good reversible coloration–bleaching effect. A typical polyethylene terephthalate (PET) foil coated with the photochromic ink could also be repeatedly printed with various patterns and displayed excellent rewritable performance over tens of cycles. This study proposes a simple method for widespread applications of WO₃‐based photochromic inks.     

A Low Curing Temperature Silver Ink for Use in Ink‐Jet Printing and Subsequent Production of Conductive Tracks

Summary: A drop‐on‐demand ink‐jet printer has been used to print a silver‐organic solution onto glass substrates. Conductive silver tracks were obtained by heat treatment of the ink‐jet printed deposits at temperatures ranging from 125 °C–200 °C in air. Resistivity values were found to have dropped to two to three times the theoretical resisitivity of bulk silver after temperatures of 150 °C and above were used.

Resistivity values of a silver‐based ink.     

Growth kinetics and morphology of self-assembled monolayers formed by contact printing 7-octenyltrichlorosilane and octadecyltrichlorosilane on Si(100) wafers

The growth kinetics and morphologies of self-assembled monolayers deposited by contact printing 7-octenyltrichlorosilane (OCT) and octadecyltrichlorosilane (OTS) on Si(100) were studied by ellipsometry and atomic force microscopy. We found that, for both OCT and OTS, full monolayers could be obtained at room temperature after printing times of 120-180 s; the printing-based monolayer assembly processes follow apparent Langmuir adsorption kinetics, with the measured film growth rates increasing both with the ambient humidity and with concentration of the ink used to load the stamp. At a dew point of 10 degrees C and an ink concentration (in toluene) of 50 mM, the observed film growth rate constant is 0.05 s(-)(1). When the printing was carried out at a lower ambient humidity (dew points of 1-3 degrees C), the measured rates of assembly were approximately a factor of 2 slower. Increasing the deposition temperature from 25 to 45 degrees C under these conditions increased the film growth rate only slightly. The morphology of the films depends on the identity of the ink. Uniform, high-coverage films could be obtained readily from the eight-carbon chain length adsorbate OCT, provided that the stamp was not overloaded with the ink; for high concentrations outside of the optimal range, the surface presented significant numbers of adsorbed particles ascribed, in part, to siloxane polymers formed by hydrolysis of the ink on the stamp before printing. In marked contrast, for the 18-carbon adsorbate OTS, the printed films always consisted of a mixture of a uniform monolayer plus adsorbed polysiloxane particles. The different film morphologies seen for OCT and OTS are proposed to result from the different transfer efficiencies of the organotrichlorosilane relative to polysiloxane hydrolysis products formed during the printing process. These transfer efficiencies exhibit sensitivities related to the permeation of the poly(dimethylsiloxane) (PDMS) stamp by the silane reagents. Short-chain inks such as OCT evidently permeate the PDMS stamp more deeply than longer-chain inks such as OTS. This difference, and the different diffusion rates of ink vs oligomeric silane hydrolysis products, determines the film morphology obtained by contact printing. The mass transfer dynamics of the process thus yield surface layers derived from varying quantities of siloxane oligomers, which subsequently transfer to the substrate along with unhydrolyzed silane adsorbate during the printing step. The structural evolution of the contact-printed films so obtained is strikingly different from that of SAMs prepared by immersion.     

Polymer‐Based Rectifying Diodes on a Glass Substrate Fabricated by Ink‐Jet Printing

Summary: The fabrication of polymer diodes on a glass substrate by an ink‐jet printing technique is reported. Both an n‐type semiconductive polymer, poly[2‐methoxy‐5‐(2‐ethylhexyloxy)‐1,4‐(1‐cyanovinylene)phenylene] (CN‐PPV), and a p‐type semiconductive polymer, polypyrrole (PPy) or poly(3,4‐ethylenedioxythiophene) (PEDOT), were printed through a piezoelectric ink‐jet printer. The printed CN‐PPV/PPy and CN‐PPV/PEDOT diodes showed good rectifying characteristics. These results indicate the potential of the low‐cost ink‐jet printing technique to produce polymer microelectronic devices and circuits.

Schematic diagram of the printed polymer diode     

Improving mechanical properties and chemical resistance of ink‐jet printer color filter by using diblock polymeric dispersants

The diblock copolymers of polystyrene and poly(tert‐butyl acrylate) (PSt‐b‐PtBA) with various molecular weights and hydrophobic/hydrophilic (styrene/acrylic acid) chain length were prepared by atom transfer radical polymerization (ATRP). Selective hydrolysis of the diblock copolymers (PSt‐b‐PtBA) resulted in amphiphilic block copolymers of polystyrene and poly(acrylic acid) (PSt‐b‐PAA). The amphiphilic block copolymers of PSt‐b‐PAA with average molecular weight (M_n) <7500 were proved to be critical in dispersing the pigments of UV curable ink‐jet inks for manufacturing the color filter. Incorporating DB2 diblock copolymer dispersants with styrene/acrylic acid ratio at 1.5 allowed more UV curable compositions in the red and blue inks without deteriorating pigment dispersing stability and jetting properties of the ink‐jet inks. The ink drops can be precisely ejected into the tiny color area. Better properties of the cured red stripe such as nanoindentation hardness and chemical resistance were found. The competing absorption of UV light by the blue pigment hindered the through cure of monomers near the interface between glass substrate and the blue stripe. This leads to lower hardness and poor chemical resistance of the UV cured blue stripe. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3337–3353, 2005     

Transparent Electrodes Printed with Nanocrystal Inks for Flexible Smart Devices

Transparent electrodes (TEs) are crucial in a wide range of modern electronic and optoelectronic devices. However, traditional TEs cannot meet the requirements of smart devices under development in unique fields, such as electronic skins, wearable electronics, robotic skins, flexible and stretchable displays, and solar cells. Emerging TEs printed with nanocrystal (NC) inks are inexpensive and compatible with solution processes, and have huge potential in flexible, stretchable, and wearable devices. Every development in ink‐based electrodes makes them more competitive for practical applications in various smart devices. Herein, we provide an overview of emergent ink‐based electrodes, such as transparent conducting oxides, metal nanowires, graphene, and carbon nanotubes, and their application in solution‐based flexible and stretchable devices.     

The use of laser desorption/ionization mass spectrometry in the analysis of inks in questioned documents

Determination of the age of a handwritten or ink printed questioned document can be an important consideration in forensic cases. Most often the age of a document is determined by the chemical behavior of the dyes that make up the ink. Exposure of the dyes to environmental factors such as oxygen and ultraviolet or visible light cause them to degrade. Often this degradation can be correlated to the time since the exposure of the ink to the elements began. A number of methods have been used to track the aging of inks on paper. This paper reports the use of laser desorption mass spectrometry as a valuable tool in not only elucidating the structures of dyes used in inks but tracking the change in their chemistry as they age. This study also explores methods for artificially aging documents using ultraviolet and visible light.     

Surface characterization of 7S and 11S globulin powders from soy protein examined by X-ray photoelectron spectroscopy and scanning electron microscopy

In this study the surface composition of 7S and 11S globulin powders from soybean proteins by aqueous buffer and reverse micelle extractions had been examined using X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Analysis by XPS revealed that the O and N atomic percentage of 7S and 11S globulin surfaces from bis(2-ethylhexyl) sodium sulfosuccinate (AOT) reverse micelle was higher than from aqueous buffer, but the C atomic percentage was lower. The O/C ratio of the 7S globulin powder from aqueous buffer and reverse micelle was similar while significant differences were obtained in the O/C ratio of the 11S globulin powder, N/C atom ratios of the 7S and 11S globulin powders and high-resolution XPS C 1s, N 1s, O 1s spectra. Powder microstructure after reverse micelle treatment showed the presence of small pores, indicating the effect of reverse micelle on the 7S and 11S globulin structure. The obtained results indicated that the reverse micelle could affect the C, O and N components on the surface of soybean proteins.     

Trace element ink spiking for signature authentication

Signature authentication is a critical question in forensic document examination. Last years the evolution of personal computers made signature copying a quite easy task, so the development of new ways for signature authentication is crucial. In the present work a commercial ink was spiked with many trace elements in various concentrations. Inorganic and organometallic ink soluble compounds were used as spiking agents, whilst ink retained its initial properties. The spiked inks were used for paper writing and the documents were analyzed by a non destructive method, the energy dispersive X-ray fluorescence. The thin target model was proved right for quantitative analysis and a very good linear relationship of the intensity (X-ray signal) against concentration was estimated for all used elements. Intensity ratios between different elements in the same ink gave very stable results, independent on the writing alterations. The impact of time both to written document and prepared inks was also investigated.     

Adsorption of glycidoxypropyl‐trimethoxy‐silane on α and β phases of titanium alloy Ti–6.5Al–1Mo–1V–2Zr

The adsorption of glycidoxypropyl‐trimethoxy‐silane (GTMS) on α and β phases of titanium alloy Ti–6.5Al–1Mo–1V–2Zr was studied. The morphology and composition of coated alloy were investigated by using field‐emission scanning electron microscopy, energy dispersive spectroscopy, and atomic force microscopy. The quantitative characterization of GTMS adsorption was carried out by using XPS. The results showed that the β phase particles exhibited better ability to adsorb GTMS molecules than the α phase, especially at lower concentrations of GTMS, which resulted in a relatively nonuniform silane coating. The differences in the adsorption ability between the α phase and β phase particles were attributed to the different alloying elements contained in them and different characteristics of the oxides formed on them. Uniform adsorption of GTMS on the overall metal surface was achieved by increasing the concentration of GTMS to 1 vol.%. Copyright © 2012 John Wiley & Sons, Ltd.     

Ink‐Jet Printing of Luminescent Ruthenium‐ and Iridium‐Containing Polymers for Applications in Light‐Emitting Devices

Summary: Defined films of luminescent ruthenium(II ) polypyridyl‐poly(methyl methacrylate) (PMMA) and iridium(III ) polypyridyl‐polystyrene (PS) copolymers could be prepared by ink‐jet printing. The copolymers were deposited on photoresist‐patterned glass substrates. Films as thin as 120 nm could be printed with a roughness of 1 to 2%. In addition, the film thickness could be varied in a controlled way through the number of droplets deposited per unit area. The topography of the ink‐jet printed films was analyzed utilizing an optical profilometer. The absorbance and emission spectra were measured using fast parallel UV‐vis and fluorescence plate reader.

Photo of the solutions of luminescent ruthenium (left) and iridium (right) containing polymers in a glass microtiter plate (top). The subsequently prepared films using ink‐jet dispensing techniques are shown below.     

光子烧结技术在印刷电子技术中的应用研究进展

光子烧结技术是一种低温、选择性、非接触式烧结技术,可以对衬底上的各种纳米材料墨水进行固化烧结,实现墨水的功能化,并获得印刷电子器件的物理性能。光子烧结技术包括激光烧结、红外烧结及闪灯烧结,它们又具有各自的应用特点,在印刷电子领域中受到了广泛的关注。本文简要介绍了光子烧结技术的一些相关研究,重点介绍了光子烧结技术在金属纳米导电墨水中的应用及研究进展。     

Applications of electrospray laser desorption ionization mass spectrometry for document examination

We have employed electrospray laser desorption ionization mass spectrometry (ELDI‐MS) to rapidly characterize certain classes of compounds – the inks within the characters made by inks and inkjet printer on regular paper and the chemical compounds within thermal papers. This ELDI‐MS approach allowed the ink and paper samples to be distinguished in terms of their chemical compositions. Sample pretreatment was unnecessary and the documents were practically undamaged after examination. The ink chemicals on the documents were desorbed through laser irradiation (sampling spot area: <100 µm²); the desorbed molecules then entered an electrospray plume – prepared from an acidic methanol/water solution (50%) – where they became ionized through fusion or ion‐molecule reactions with the charged solvent species and droplets in the plume. Copyright © 2009 John Wiley & Sons, Ltd.     

Studies into the Early Degradation Stages of Cellulose by Different Iron Gall Ink Components

Selective fluorescence labelling of oxidized cellulose functionalities followed by GPC-MALLS was used to get a deeper insight into ink-induced degradation processes. As the method is very sensitive towards oxidation and molecular weight changes, slight variations at the very beginning of aging processes, e.g. during ink corrosion of cellulose, can be studied. Five different ink modifications were applied on model papers and underwent mild accelerated aging at 55 °C and cycling humidity (7 days) followed by a short period of static humid aging at 80 °C (2 days). Pure ink constituents like tannic acid or iron sulphate do not result in the same degree of oxidation or chain scission as complete inks. Balanced ink degrades paper more than single compounds, but less than unbalanced inks. Interestingly, some degradation occurs already during or shortly after the application process of unbalanced inks on paper. It could be demonstrated that this oxidation proceeded in a rather high Mw area, while the subsequent aging steps affected predominantly regions of shorter cellulose chains.     

液态金属印刷电子墨水研究进展

印刷电子是一种基于印刷原理的新兴电子增材制造技术,与传统电子加工方法相比,它在大面积、柔性化、个性化、低成本制造电子等方面具有无可比拟的优势。印刷电子所用的典型导电墨水通常分为三类：碳系、高分子及金属导电墨水,然而它们在打印后仍需借助高温后处理工艺,以进一步提升打印物及墨水的电导率及运行可靠性,步骤稍显繁琐;且由于相应纳米材料及墨水的配制较为复杂,也增加了使用的成本。液态金属作为一大类新出现的电子打印墨水,近年来正日益成为重要的研究领域,这种墨水具有电导率高、制备简单、无需后处理等独特优点。为推动这一方向的研究,本文评述了国内外围绕液态金属导电墨水物理化学性质的研究进展及对应的典型打印方法,并指出了进一步发展的方向。