This was Tom and Martin's fourth MarathonTalk run camp down in the New Forest and my second. I was really looking forward to it after last year. I hardly ever do this sort of thing - the only other one I can remember going to in fact was years ago with Runners World - but last year's was excellent and this one looked even more full of events.
It's hosted by the curiously-named Sandy Balls - which no matter how many times you say it, teases out the schoolboy humour you've tried to suppress all your adult life.
People have come a fair old distance to get here and all have tales of horror of a Friday night stuck on the M25 or similar but nobody is regretting the trip as we huddle round some braziers supping coffee until someone helpfully points out there's a bar.
Lots of familiar faces from last year's event and Twitter and some have been to all four so it has a loyal following. Also Martin kindly used my event booking service to sell it so I know it sold out in a few days. Get in fast next year, folks!
I missed the Friday night and Saturday morning last year, arriving late, so this time was determined to make it to the local ParkRun (Moors Valley) which traditionally kicks the weekend off. My ParkRun attendance record is pretty shocking despite signing up almost from the off. I've only run 9!
I used www.rowmaps.com which looks like hell but is actually a really good resource for footpaths/greenways/bridleways etc. and came up with this..
We met at reception at 7 as the temperature hovered around zero, fired up the Suunto and headed off out to Moors Valley. What a great run! I love this sort of thing. A mini adventure where you don't know what's around the next corner. We're chatting away and it seems to take about 5 minutes. But there's lots of leaf-strewn trails and forests and wildlife with only an unavoidable, but short, stretch of road to get in the way and I could have run that all day.
The toasty warmth built up from that run dissipates disappointingly quickly as we're waiting for the ParkRun kick off - we turned up about 15 minutes early - as the Camp party boosts the turnout by a good 100 people. The joint mobility seems to have gone the same way as the warmth and I start at a snail's pace but gradually pick it up as life returns once again. Nice course! Wide forest trails, lakeside paths. I ended up on the finishing 500m trailing some young lad who was going for it so I gave him some cheery encouragement only to accidentally step on the back of his shoe and nobble his race. Oh well. Life is hard!
There's time for a shower before the weekend event opens properly with everyone congregating in the function room but there's another running session coming up so I don't bother despite smelling faintly of cow pats.
Martin and Tom kick things off and then there's an interesting chat on motivation with Andy Lane and Liz. Always good to hear the elite field suffer with the same pre-match nerves as the rest of us!
Then there's a speedwork session a mile up the road which is a new format to me. 1000m at 80% effort, 15 seconds rest then 300m hard with a further rest before three more of those. I jogged up to the start and my legs were pretty heavy so I decided to do my own thing and did some short hill reps instead in the same area which brought the total up to around 20 miles for the day.
Somehow I'd only eaten a sausage bap all day so the buffet dinner was a food oasis in a starvation desert and I demolished a vast amount. You get pretty well fed here. Two meals are included and they're not stingy.
More entertaiment from Vassos Alexander talking about - yes - running preceeded the quiz. I'm aware I'm very lightly brushing over all the content here but there's so much going on, no-one's going to read this post if I go into any more detail!
The less said about the quiz the better. I thought we had a decent team. I thought I knew stuff. I especially thought I knew stuff about running and that was 90% of the rounds. We even had Lucy who does PR for running brands! But the night ended in ignominy and second last - saved from a near zero score by a ridiculously easy picture and music round that someone who'd never seen a picture before could have had a decent stab at. I drowned my shame in a pint of Ringwood's Razor Back. It takes several pints to drown shame it turns out.
I ducked out of the last item on the agenda - a headtorch run at 11pm+ mainly because my legs were barking but there was also something about the Razor Back / Jogging combo that seemed like a bad idea.
So to Sunday.. and another run in the New Forest! And another run I managed to duck out of - I seem to have done a lot of my own thing this weekend and that is one of the features of the camp. You can do as much or as little as you like. This was an interesting 10 miler where you had to finish by 12pm at the latest and set off so you did so as close to 12 as possible. To be honest I didn't understand the rules when it was explained to me (though everyone else seemed to) and still don't now but a handicap race basically.
If you didn't want to do that you could run either 8 or 16 miles (one or two laps of a trail route) with Hayley Yelling - yet another elite athlete on hand - or, as I say, do your own thing. My legs weren't up for a fast 10 so I didn't formally enter the handicap race but ran anyway thinking I'd add some miles on. The legs weren't thanking me though so in the end I rolled in at 12:04 and therefore I suspect last - but that racked up 34 miles for the two days with some speed and some hills so very worthwhile.
The New Forest is a lovely place to run and we only scratched the surface. This 10 was the route of the Heartbreaker Half Marathon which is well worth doing (is it still on?) - great training for a full!
Yet again I'd eaten nothing at all which is ridiculous but was saved by the carvery which was a full on pile your plate high affair and I took full advantage before the camp was brought to a close and I caught the end of the rugby with Dan before heading back up the M3.
A really great weekend! There is such a good, positive vibe about it. You meet lots of like-minded people, get to speak to the training experts and elite and most importantly get to run in some fantastic countryside.
I think the camp is great value too including as it does a couple of large meals and 3 nights of accommodation plus all the extras. Highly recommended - but as say, get in quick, it goes fast!


"Ashes to ashes... California- The book of Abraham the Mage holds the secret of eternal life a secret more dangerous than any one man should possess. Dr. John Dee is two pages away from the knowledge that would bring the Dark Elders into ultimate power and could mean the destruction of the world as we know it. Two people stand in his way- Josh and Sophie Newman. Paris- Time is running out for Nicholas Flamel and his wife Perenelle. Every day they spend without the book, they age one year- their magic becomes weaker and their bodies more frail. Niccolo Machiavelli, immortal author and celebrated art collector, works for Dee and is in hot pursuit of them Flamel knows there s no time to lose and Sophie must learn about Fire Magic Josh and Sophie are the world s only hope. If they don t turn on each other first."
Dark magic and fast-paced adventure in this second book in the New York Times bestselling series The Secrets of the Immortal Nicholas Flamel. Now published with an exciting new cover look and introduction from the author!


With a reputation for high quality, precision engraving, Fine Cut were awarded the honour of laser engraving the prestigious London Football Awards for the 2018 ceremony.
Articles Is laser labelling the future for food?
M&S has announced plans to label its fruit using 'tattooing' technology.
Articles Ever wanted to personalise your iPad or Kindle?
If you fancy giving your prized piece of technology a personal touch, give us a ring today to see how we could personalise your device!
Articles Engraving and embossing: A more permanent labelling solution?
Engraving and embossing products might be a more durable alternative to adhesive labels.
A ring that might have been the inspiration behind JRR Tolkien's 'Lord of the Rings' and 'The Hobbit' books has gone on display in Hampshire, guardian.co.uk reports.
The Royal Society of Literature made use of TS Eliot's fountain pen yesterday (18 March) for the first time since the playwright and poet's death, londonist.com reports.
The Earl of Wessex is to unveil a new bronze-engraved portrait of his mother, the Queen, in Winchester today (29 January), hampshirechronicle.co.uk reports.
The John Rylands Library has 350 newly rediscovered engravings by the poet William Blake that it will be exhibiting from February.
Famous props from the 1956 Hollywood epic 'The Ten Commandments' have been sold for almost £40,000 at an auction in California, news-panel.com reports.
Olympic distance runner, Mo Farah has announced he will have the names of his new twins engraved on his gold medals.
A glass engraving exhibition is to be held in Stourbridge's Red House Glass Cone and will feature artefacts which are set to take pride of place in Downing Street, stourbridgenews.co.uk reports.
A new watch launched to coincide with the release of 'The Dark Knight Rises' has celebrated its association with the film via an engraving.
Engraving tools with business names or work postcodes helps make them more easily traceable, police have pointed out.
The Lithuanian Olympic squad will be presented with a unique flag featuring engraved names of its supporters shortly before jetting off to London.
A pair of Cardiff University students are set to wed after a proposal involving an engraving at Wales' Millennium Stadium.


I have written to Malkin Falimede and have done as you have asked. CrIsis and I have decided to take on the Manus Trebelium head on and have attached the location of his base to this message. I strongly feel that you and the rest of the army of Timiro should come and counter attack Manus with us. Evacuate Fort Calda and save its citizens. Let us together cut off the head of this snake. Meet up with us there in approximately twenty-four days if we do not run into any delays. Please keep us up to date with your status. How many days out would you like us to send another pigeon? If you could also send word, I would like King Gedro to come. If you must, feel free to use the name General Mordox if it will get him to come. Tell the king that I have gone to take out this enemy of Timiro and seek any aid he would offer. Together we will crush this force. Please gather any druid friends you can or remaining resistance. I feel this is the fight that we will finally earn our freedom. I hope that our king's eyes will be open after this fateful battle. If not, I fear it never will and my death will follow shortly.
Posted by Gavin on the 16th of Corg in the 9th Year of King Gedro.


#4 Size Bells - Most Traditional Sounding with the Deepest Tone with one bell on Strap.
Overall Length: 5 3/4 inches.
If I could give you ten stars I would! Beautifully made! What I love most are the bells. It's the sound of Christmas and snow. Everything that is magical here in Vermont where I live.
Please don't hesitate in buying these! I promise you won't be disappointed.
These are top quality bells with a melodious tone (esp the deep tone). It is a nice way to keep track of whenever someone enters the room. Makes a lovely gift, and the overall workmanship of this item is outstanding.


text:
Mechanical breathing in organic electrochromics
Xiaokang Wang ORCID: orcid.org/0000-0002-5636-23131,
Ke Chen2,
Luize Scalco de Vasconcelos ORCID: orcid.org/0000-0002-4111-56191,
Jiazhi He2,
Yung C. Shin1,
Jianguo Mei ORCID: orcid.org/0000-0002-5743-27152 &
Kejie Zhao ORCID: orcid.org/0000-0001-5030-74121
Nature Communications volume 11, Article number: 211 (2020) Cite this article
The repetitive size change of the electrode over cycles, termed as mechanical breathing, is a crucial issue limiting the quality and lifetime of organic electrochromic devices. The mechanical deformation originates from the electron transport and ion intercalation in the redox active material. The dynamics of the state of charge induces drastic changes of the microstructure and properties of the host, and ultimately leads to structural disintegration at the interfaces. We quantify the breathing strain and the evolution of the mechanical properties of poly(3,4-propylenedioxythiophene) thin films in-situ using customized environmental nanoindentation. Upon oxidation, the film expands nearly 30% in volume, and the elastic modulus and hardness decrease by a factor of two. We perform theoretical modeling to understand thin film delamination from an indium tin oxide (ITO) current collector under cyclic load. We show that toughening the interface with roughened or silica-nanoparticle coated ITO surface significantly improves the cyclic performance.
Organic electrochromic devices (OECDs) emerge in the avenues of smart windows1,2,3,4 and displays5,6,7,8 and present major advantages such as short switching time9, multicolor capabilities10, ambient solution processing11, and low cost12. OECDs are typically composed of five stacking layers: a transparent current collector, an electrochromic layer, an electrolyte, an ion storage layer, and a second transparent/reflective counter electrode3. During bleaching/charging, the applied voltage drives electron extraction from the electrochromic layer (p type) with a change of its absorption band, which bleaches the polymer film13. Meanwhile, counterions intercalate into the electrode film to maintain electroneutrality14,15. The electrostatic force and mass transport collectively cause expansion in volume of the film16. The electrochemical process is reversed during electrochromic coloring/discharging. OECDs in practice often requires a stable cycling for hundreds of thousands of times. Over cycles, a repetitive size change of the electrochromic layer—volumetric expansion during bleaching and shrinkage during coloring, termed as mechanical breathing, persists and eventually leads to material fatigue and structural disintegration of OECDs. The interfacial incompatibility and detachment during operation17,18 become a key factor limiting the quality and lifetime of OECDs and present an obstacle to the large-scale use of OECDs19.
Material deformation associated with redox reactions in electrochemical systems is well studied in the past couple of decades20,21,22,23. However, quantification of such chemomechanical process in situ in polymer thin films remains a grand challenge, because of the softness of the organic polymers, the complexity of the chemical composition, the challenge of measurement down to the submicron scale, and the difficulty to monitor the multilayer device in a real-time operation. The reported values of volumetric strain of polypyrrole upon redox reactions have been found in the range of a few percent to a few hundreds of percent24,25,26. This huge variation comes partially from the inaccuracy of the probing technique. For instance, using the servo-controller, tensile force inevitably builds up in thin films against gravity which compromises the measurement of the actual deformation26. On the other end, the electrochemistry strain microscopy is sensitive to local environmental noise and might overlook the macroscopic deformation27. There is a need of an accurate yet facile method to detect the chemomechanical strain in redox active polymers in situ and in operando.
The change of the material state in the redox reactions often induces a mechanical breathing strain and a dynamic change of the mechanical properties of the polymers, although there is little consensus in existing studies on how the mechanical behavior quantitatively evolves over electrochromic processes. Previous measurements of the mechanical properties of poly(3,4-ethylenedioxythiophene) (PEDOT) using acoustic impedance showed that the shear modulus was sensitive to the doping level28,29,30, temperature28,29, electrolyte28,29, crosslinker31,32, and even film thickness33. Ispas et al.28. concluded that anion insertion stiffened the PEDOT film while cation expulsion caused softening. This contradicts the recent finding by Wang and co-workers via electrochemical quartz crystal microbalance with dissipation (EQCM-D)15 that the poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl) film softens with an increase in mass while the material is in 0.5 M LiCF3SO3. It is worth noting that both the acoustic impedance and the EQCM-D measurements are based on presumed knowledge of the compositional fraction or the stress–strain constitutive relationship of the material. A direct method without assuming the material behavior will be advantageous to measure the mechanical properties of redox active polymers.
In the multilayer structure of OECDs, the breathing strain in the polymeric thin film is bounded by the underneath inactive substrate, typically the current collector indium tin oxide (ITO). This mismatch induces mechanical stresses in both the film electrode and the substrate. Sen et al.34 employed multibeam optical stress sensor and showed that the stress in the polypyrrole-electrode double layer accumulated to be over 15 MPa after 50 redox cycles. The growth of the bulk stress in the organic film as well as the interfacial stress between the soft polymer and the hard substrate can cause bending of the thin double layer, wrinkling of the film electrode, crack at the interface, and debonding of the thin film from its electron conduction network. Although tremendous efforts have been placed in synthesizing new materials and modifying the interfacial adhesion4,17,35,36,37,38,39,40, the mechanistic understanding of the damage initiation and evolution in organic thin film electrochromics remains elusive. The rational design of OECDs of enhanced mechanical reliability requires careful analysis on the generation of mechanical strain, the growth of stresses, the translation of mechanical failure into the degradation of device performance, and then a guidance of design to identify key parameters to optimize in future experiments.
Here we use the well-documented poly(3,4-propylenedioxythiophene) (PProDOT) as a model system to study the mechanical breathing strain upon the redox reactions and the failure at the interface of the device. Moreover, the methodologies and understanding can be referenced to a large library of high-performance electrochromic materials made of PProDOT. We use the environmental nanoindentation to determine the volumetric strain of PProDOT thin films during electrochromic switching in the liquid electrolyte and then to measure the mechanical properties in the reduced and oxidized states. The thin film electrode expands up to 30% in volume upon oxidation and both elastic modulus and hardness decrease by a factor of two. We then perform computational modeling to examine the stress field and interfacial failure between an ITO current collector and the film. The stress concentration initiates an edge crack, which continuously enlarges toward the center of the film driven by the shear cracking during oxidation and a mixed mode of shearing and opening crack during reduction. The damage evolution is in excellent agreement with our in situ observation. We use the dimensionless quantities of the breathing strain and the crack driving force to draw a phase diagram to delineate the safe and delamination zones. To demonstrate the design principle of the electrochromic electrode, we show that toughening the interface with roughened or silica-nanoparticle coated ITO surface increases the cyclic life of PProDOT films by nearly two orders of magnitude.
Mechanical behavior of PProDOT upon electrochromic reactions
We sketch the interfacial delamination in organic thin film electrochromic devices and its impact on the cyclic performance in Fig. 1a. The mechanical debonding of the film electrode from the current collector limits electron and counterion transport and impedes electrochromic switch of the film upon cycles—at the oxidized state, the delaminated regimes retain positive charges and counterions and therefore remain their bleaching state in the following reduction reaction, while the intact regimes maintain electron and counterion transport and enable chromic switching. Supplementary Movie 1 shows the mechanical breathing and interfacial delamination of a PProDOT film after around 160 cycles by in situ optical observation. The repetitive deformation and the partial debonding of the film are visible by bare eyes. The optical microscope is located within a glovebox filled with argon. The inert environment avoids contamination of moisture and oxygen to the liquid electrolyte. Figure 1b shows a few snapshots of the film morphology after every 60 cycles starting from its pristine state. The repetitive change in size of the PProDOT electrode upon redox reactions eventually leads to the failure of the electrode at the interface.
Fig. 1: Sketch of interfacial delamination in thin film electrochromic devices.
a The mechanical delamination from the current collector limits electron and counterion transport and impedes chromic switch of the film upon electrochemical cycles. b Experimental observation of mechanical breathing of PProDOT film and its morphology after every 60 cycles. The thin film experiences repetitive expansion and shrinkage in volume in the redox reactions which ultimately leads to the failure of the device at the interface.
We use customized nanoindentation to measure the breathing strain in PProDOT film on ITO via targeted indentation and scratch test. Figure 2a shows the schematic of the methodology, where dfilm denotes the travel displacement of the tip when the contact between the tip and the film is detected, and dITO represents the tip displacement down to the ITO substrate. To eliminate the effect of the liquid flow, all the electrodes are firmly attached to a homemade fluid cell41. The abrupt change in the contact stiffness when the tip approaches to the surface, Supplementary Fig. 1, indicates the surface contact. For the targeted indentation, we sample a series of indentation points across the boundary between the film and the substrate. Possible effect of sample tilting is leveraged. The tip displacement dfilm or dITO for each targeted indentation is recorded and is shown in the upper panel of Fig. 2b. The step height represents the thickness of the film. This method eliminates penetration of the tip into the sample, as is occasionally observed in the scratch test. For this non-standard method, we use atomic force microscope (AFM) to validate the targeted nanoindentation for the dry sample. The AFM images (Supplementary Fig. 2) are taken at the same locations where indentation tests are performed. The thicknesses measured by the two methods are listed in Supplementary Table 1. The good agreement demonstrates that the targeted indentation measurement is reliable. Another independent measurement is done by the scratch test. We use the embedded G-Series Ramp Load Scratch with Topography Compensation method in the instrument. The tip profiles the surface with a very small load (1–3 µN) along a straight line crossing the boundary between the film and the substrate. The tip displacement versus the scratch distance is shown in the lower panel of Fig. 2b. Again, the step height gives the thickness of the film. Note that, the film pile-up near the boundary between the film and the substrate may bring in artifacts in the measurement and the tip may end up crashing on the film from the side. The local surface detection in this case is not accurate. Here we only use the data marked in the cyan box in the case of targeted indentation, away from the boundary, to interpret the film thickness.
Fig. 2: In situ thickness measurement.
a Sketch of the thin film thickness measurement by the environmental nanoindentation method. dfilm (dITO) denotes the travel displacement of the tip when the contact between the tip and the film (ITO) is detected. b Thickness of PProDOT in the pristine and oxidized states. The upper panel shows tip displacement measured by targeted indentation. The lower panel shows the tip displacement in the x-direction measured by the scratch test. For both methods, the step height denotes the thickness of the film. c A volumetric strain εV in the range of 20–30% is determined for PProDOT upon oxidation using the scratch and targeted indentation methods.
With the two methods described above, we measure the thickness of the film at the same locations in the pristine and oxidized states in the first cycle. The nanoindentation sites are chosen ~50 um away from the edge to avoid possible interference of film delamination from the substrate. As seen in Fig. 2b, the film surface is clearly elevated upon oxidation indicating an increase of the film thickness. For each measured location, we compare the thickness of the film before and after oxidation, (h0, h). Since the in-plane deformation of the film is bounded by the hard substrate, the volumetric strain is calculated by εV = (h − h0)/h0. Figure 2c shows the results of the measured volumetric strain with the average and standard deviation, the median, and the 25–75% range of the data. The volumetric strain is found to be 26.4% by targeted indentation, 30.9% and 23.1% by scratch test for the tip profiling velocity of 10 µm s−1 and 1 µm s−1, respectively. This overall volumetric strain gives a roughly 10% linear strain for a homogeneous and isotropic material. The deformation is recoverable if the strain is within the elastic limit and if the induced stress does not exceed the material yield strength42. From a microscopic perspective, the polymer chains are entangled in nature. A tensile stress elongates the bulk polymeric material by stretching the serpentine chains to a straight configuration followed by interchain slip. The intrachain elongation is often recoverable upon removal of the external load, while the intrachain slip manifests as the permanent deformation43,44. For the PProDOT film we study here, the averaged molecular weight Mn = 9900 suggests that the molecular chain is made of ~30 monomers, which corresponds to an end-to-end length of less than 10 nm. It is most likely that the interchain slip accommodates the large volumetric change of the film in the redox reaction rather than the intrachain elongation. This fact indicates that the plastic flow is invoked upon oxidation when the counterions and solvent molecules insert into the film. In the course of reduction, the counterions and solvent molecules are expelled from the host and the polymer coils aggregate by the interchain interactions.
We perform nanoindentation to measure the elastic modulus and hardness of the PProDOT film in the pristine state (dry and in PC, respectively), reduced state (in electrolyte), and oxidized state (in electrolyte) using the continuous stiffness measurement (CSM). The load–displacement response is shown in the upper panel of Fig. 3a. A harmonic oscillation of 2 nm at 45 Hz is superposed during loading, such that the modulus and hardness can be determined as a continuous function of the indentation depth. We have eliminated the substrate effect using the prior-established model45. The lower panel of Fig. 3a shows that the modulus and hardness decrease as the indentation depth increases. This behavior is typical for a soft film on a hard substrate and is consistent with several prior studies46,47,48. Here we use the data in the plateau region marked in the cyan box to determine the average value. We measure the material properties of the pristine sample in both dry and wet states (in propylene carbonate for 2 h) to eliminate the potential effect of the liquid environment. The results of the pristine sample are consistent but the measurement in the liquid environment seems less spread, Fig. 3b. The same procedure is employed to determine the elastic modulus and hardness of the film after oxidation. It is striking that both the modulus and hardness decrease by nearly a factor of two when the film is oxidized as shown in Fig. 3b. And the electrochemical conditioning process, by comparing the data of the 1st and 100th cycles, has limited effect on the mechanical properties. This drastic decrease in the mechanical properties might be counterintuitive. The mechanical response is related to the change of the state of charge and the microstructural feature of the polymer chains. Upon oxidation, the neutral chains lose electrons and morph into a quinoid structure49. A stiffer backbone is then expected due to the nature of quinoid structure upon charge delocalization. The experimental results indicate that (1) the intermolecular interaction is mostly responsible for the mechanical response of the film, and (2) the intercalation of counterions and solvent molecules weakens the intermolecular interactions among the loosely entangled polymer chains. We are pursuing atomistic modeling to examine the local bonding environment, the long-range intermolecular interactions, and microstructural evolution to fully understand the polymeric material behavior upon redox reactions.
Fig. 3: Mechanical properties of PProDOT film.
a Upper panel: the load-displacement curves of indentation on the pristine and oxidized PProDOT films. Lower panel: Modulus and hardness of the pristine and oxidized PProDOT as a function of the indentation depth. b Modulus (upper panel) and hardness (lower panel) of PProDOT in the pristine and dry state, the pristine state in PC, the oxidized state in electrolyte after the 1st cycle, the reduced state in electrolyte after 100 cycles, and the oxidized state in electrolyte after 100 cycles.
Mechanistic understanding of electrochromic film delamination
With the experimental input of the breathing strain and the mechanical properties of PProDOT, we conduct finite element analysis (FEA) to understand the stress field and the crack initiation and growth in the organic thin film electrochromic devices. We use an elastic-perfectly plastic constitutive relationship to describe the PProDOT film. The elastic modulus is taken from the experimental results in Fig. 3, and the material yield strength is assumed to be one third of the hardness. To mimic the volumetric expansion upon oxidation, an isotropic thermal strain up to 10% is applied to deform the film. The polymeric film expands against the constraint provided by the substrate. The interaction of the film–substrate system at the interface is described by a traction-separation law of a trapezoidal shape (Supplementary Fig. 3). When the contacting points start to separate, the interfacial traction increases linearly with a stiffness Ki until it reaches the traction limit Tic. Here i denotes the normal (i = I) or tangential (i = II) load. The damage function D remains 0 within the elastic regime and starts growing when T = Tic. Following the elastic load, the interfacial traction maintains a constant to mimic the plastic flow of the film. When the dissipated energy Gic (shaded area in Supplementary Fig. 3) is equal to the interfacial toughness Γ, the traction reduces to 0 and the interface is fully separated (D = 1). Detailed description of the traction-separation law can be found in Supplementary Note 1.
FEA results show that oxidation of the film leads to the concentration of shear stress around the free edge between the film and the substrate, as shown in the contour plot, left column of Fig. 4. Once the shear stress exceeds the interfacial strength, the interfacial damage initiates and grows, as is evident in the correlation between the damage function and the shear stress distribution in Supplementary Fig. 4a. The different lines in Supplementary Fig. 4a represent the various degrees of oxidation with ε = 0.1 representing the complete oxidation. When the oxidation reaction proceeds, the film continues to expand with a steady growth of the interfacial crack. The normal stress associated with the oxidation reaction remains compressive, therefore the damage is driven by a pure shearing crack (mode-II). In the following reduction reaction, the PProDOT film shrinks in volume against the interfacial adhesion. The stress field within the film starts to change with an elastic unloading and succeeds by an opposite shear stress and a positive normal stress. The positive normal stress is a result of the plastic flow of the film50. Supplementary Fig. 4b shows the evolving shear stress at the interface in an oxidation and reduction cycle. The contour plots of the shear stress and normal stress in different cycles are shown in the middle and right columns of Fig. 4. In the process of the reduction reaction, the interfacial damage is driven by a mixed mode of shearing and opening cracks. The positive out-of-plane normal stress is the reason to cause the bending of the film and delamination from the substrate. From the computational results we understand the dynamics of the interfacial damage as follows: the breathing strain induces a mismatch strain in the film and the substrate; the constraint of the substrate causes concentration of stresses at the free edge; edge damage emerges as the stress exceeds the interfacial strength; the edge crack continuously grows toward the center of the film driven by shearing crack during oxidation and a mixed mode of shearing and opening crack upon reduction. The damage evolution in the finite element modeling agrees very well with the in situ optical observation as shown in Fig. 1b and in Supplementary Movie 1.
Contour plots of the shear stress τxy in PProDOT at the oxidized state, τxy at the reduced state, and the normal stress σy at the reduced state after the 1st, 4th, and 8th cycles, respectively. Deformation is drawn in the actual scale.
To draw the complete portrait of the interfacial damage in the electrochromic electrodes, we examine more closely the dynamics of the damage initiation, crack opening, and propagation. In the early stage of cycle, the interface remains intact for the regime away from the free edge. As the redox reaction proceeds, the stress in the delaminated zones is released, and the stress concentration and mechanical damage are progressively translated toward the center of the film. The intact area, the damage zone where the film and the substrate are partially separated, and the cracked regime are outlined in the upper panel of Fig. 5a. The figure also shows the shear stress profile and the interfacial damage function along the interface after the 4th oxidation reaction. The lower panel of Fig. 5a plots the size of the damage zone and the size of the crack length, normalized by the initial film thickness, as a function of the cycle number. The crack opening is an irreversible process. We observe that the size of the damage zone reaches a nearly constant value after the initial oxidation reaction albeit the stress field alternates quite dynamically afterwards. The size of the cracked zone, on the other end, increases almost linearly starting from the first reduction reaction up to the 8th cycle. This is understood due to the combination of the reversible breathing strain in the redox reactions and the plastic deformation of the film—the collective factors result in pretty much the same magnitude of the stress field except the difference in the sign of the stresses in the oxidation and reduction processes. In addition, the shear stress generated at the interface is a dominating factor driving the film delamination. Therefore, the cracked regime increases linearly in size, separated by a nearly constant damaged zone from the intact area, over cycles.
Fig. 5: Damage analysis of PProDOT thin film upon redox reactions.
a Upper panel: Sketch of the shear stress profile (left y axis) and the interfacial damage function (right y axis) along the interface after the 4th oxidation reaction. Lower Panel: The evolution of the crack length (magenta dots), c/h0, and the size of the damaged zone (blue dots), D/h0, as a function of the cyclic number of the redox reaction. b A phase diagram of interfacial delamination in electrochromic thin film in the space of the dimensionless breathing strain and interfacial toughness. The solid spheres represent the numerical results, while the line is drawn to delineate the boundary between the intact and delaminated conditions.
We construct a phase diagram to guide the design of the thin film electrochromic devices of enhanced mechanical reliability. By intuition, the mechanical damage depends on the breathing strain εV = (h − h0)/h0 for a thin film bounded by a substrate. Crack initiates at the interface when the driving force, the energy release rate, exceeds the interfacial toughness. The energy release rate for a thin film subject to the shear yielding is calculated as \(G = Z \cdot \frac{{\tau _{\mathrm{c}}}}{E} \cdot \tau _{\mathrm{c}} \cdot h_0\), where Z is a dimensionless parameter describing the geometric effect, τc is the shear yield strength, E is the elastic modulus, and h0 is the film thickness. For the initiation of debonding of thin films, Z = 1.02651. The dimensionless parameter, \(\frac{{{\it{\Gamma }}E}}{{Z\tau _{\mathrm{c}}^{\mathrm{2}}h_0}}\), the interfacial toughness Γ normalized by the energy release rate G, describes the competition between the crack driving force and the crack resistance. Figure 5b shows the computational results of the critical conditions to cause film delamination in terms of the dimensionless breathing strain εV = (h−h0)/h0 and the material parameters \(\frac{{{\it{\Gamma }}E}}{{Z\tau _{\mathrm{c}}^{\mathrm{2}}h_0}}\). The solid spheres represent the numerical results, while the line is drawn to delineate the boundary between the intact and delaminated conditions. The phase diagram offers design rules to maintain the structural integrity of the thin film electrochromic devices. Interfacial damage will less likely happen by (1) minimizing the breathing strain in the redox active thin films, (2) enhancing interfacial toughness Γ, (3) utilizing materials of a higher elastic modulus E and a lower yield strength τc, and (4) reducing the film thickness h0. In short, the general guideline is to use small-size, stiff (high modulus), and soft (low yield strength) film electrode, and tough interfacial adhesion.
Interfacial engineering for enhanced mechanical reliability
For the fabrication and device performance, the thickness of the film electrode is often chosen to maximize the optical contrast between the two redox states. Among the rules offered by the phase diagram, the interfacial toughening by physical or chemical modification seems most practical. While providing enhanced adhesion, the modified interface should be highly transmissive, have good electron-transport properties and remain of low cost. Current strategies include chemical bonding, physical bonding, and surface roughening to enable mechanical interlock of the film and the substrate. Here we demonstrate that by grinding the pristine ITO surface using sandpaper and by coating the interface between the current collector and the polymeric film with silica-nanoparticles (SiO2 NP), the cyclic life (when current density > 0.15 mA cm−2, Fig. 6f–h) of the electrochromic electrode is promoted considerably as compared to the bare ITO electrode (by nearly two orders of magnitudes for SiO2 NP-treated ITO), Fig. 6a–e.
Fig. 6: Interfacial modification of electrochromic electrode.
a The surface treatment and improvement of interfacial contact considerably enhance the cyclic performance of OECDs. (b)-(e) show the images of the as-prepared PProDOT film on bare ITO, PProDOT on bare ITO after 140 cycles, PProDOT on roughened ITO after 380 cycles, and PProDOT on SiO2 NP treated ITO after 8500 cycles, respectively. The cyan dot lines indicate the electrolyte front line. (f)–(h) show the cyclic voltammetry responses of PProDOT film on bare ITO, roughened ITO, and SiO2 NP-treated ITO, respectively.
The PProDOT thin film electrodes start from the same condition (morphology and interfacial conductivity), as indicated from the pristine state of electrodes (Fig. 6b) and similarly among the first-three cyclic voltammograms (CVs) cycles in both shape and the current density (Fig. 6f–h). The CVs of PProDOT thin films on both the bare ITO and modified ITOs show a pair of redox peaks at 0.56 V and 0.29 V and the same onset of the oxidation potential of ~0.4 V, which indicates that the surface modifications have negligible effects on the electrochemical characteristics of PProDOT thin films. The current density for all three electrodes gradually drops in subsequent cycles, possibly due to micro-scale delamination and ion trapping52 untill obvious film delamination is observed. The PProDOT film on bare ITO is severely damaged after 140 cycles (Fig. 6c), leaving only the magenta part in contact while the remaining region being peeled off and dysfunctional. The charge density quickly drops from 4.87 mC cm−2 to 1.8 mC cm−2. Part of the PProDOT film on roughened ITO is delaminated after 380 cycles and reaches the same electron density of 1.8 mC cm−2 from 4.75 mC cm−2 (Fig. 6d). In contrast, the PProDOT film on SiO2 NP treated ITO starts with an electron density of 4.62 mC cm−2 and sustains over 8500 cycles before its current density decreases to the same value of 1.8 mC cm−2. In this case, it seems that only minor delamination occurs as observed at the end of cycles (Fig. 6e). The interface damage is also evident by the drop in the current density as shown in Fig. 6f, g.
The improved durability is attributed mostly to the increased surface roughness of the ITO which enables mechanical interlock and reinforces the adhesion of the film53. This is demonstrated by the surface morphology and roughness of the bare ITO, ITO ground by sandpaper, and SiO2 NP coated ITO in Fig. 7 and Supplementary Fig. 5. The bare ITO has the finest surface with a root mean square height of only 5.51 nm, followed by SiO2 NP treated ITO surface (21.9 nm). The nanoparticles (diameter of ~200 nm) self-assemble into a well-packed hierarchical nanostructure, as shown in the 3D AFM image in Fig. 7d and in the SEM images in Supplementary Fig. 6. Nanoscale inter-particle gaps (white arrow in Supplementary Fig. 6b) introduces high-density mechanical interlock between the polymer film and the substrate, which significantly improves the performance. Note that the mud cracks (red arrows) in Supplementary Fig. 6a and 6b are formed by the electron-wind forces at high magnification and are absent from the modified electrodes. Due to the size of the abrasion particle on sandpaper, the roughness of the ground ITO surface varies from 29.2 nm to 620 nm. The characteristic size in ground ITO electrode is in the micron scale, rendering a less dense mechanical interlock and less improved cyclic life. In addition to the surface roughness, SiO2 NP can also change the physical properties of the ITO surface which benefits the interfacial adhesion35,54.
Fig. 7: 3D surface morphology of the ITO surface.
a Bare ITO. b A flat region in roughened ITO. c A scratched region in roughened ITO. d SiO2 NP-treated ITO. Sq denotes the root mean square height roughness.
In summary, we employ customized environmental nanoindentation to probe the breathing strain of electrochromic thin films in situ upon cyclic redox reactions. The PProDOT film deforms up to 30% in volume in the oxidation and reduction processes. The variation of the state of charge alters the elastic modulus and hardness by a factor of two and the film becomes softer and more compliant in the oxidized state. We perform theoretical modeling to understand the damage initiation and propagation at the interface of electrochromic layer and the current collector. The mechanical breathing of the redox active film induces major stresses near the free edge between the film and the substrate. Edge crack emerges when the mismatch stress exceeds the interfacial strength. The oscillatory load, resulted from the repetitive size change of the film in the redox reactions, alters the stress field, and leads to a linear progression of film delamination toward the center over cycles. The breathing strain in the electrochromic film and the dynamics of the interfacial damage are in excellent agreement with the in situ optical observation. We construct a phase diagram, in terms of the dimensionless quantities of the breathing strain and the material parameters, to guide the design of the thin film electrochromic devices of optimum mechanical stability. We demonstrate the design rules by toughening the interface with roughened or silica-nanoparticle coated surface which results in an elongated cycle lifetime of nearly two orders of magnitude compared to the untreated sample.
The PProDOT was synthesized via direct arylation polymerization using a previously reported procedure55. The molecular weight was characterized by gel permeation chromatography. Then PProDOT was dissolved in chloroform and stirred overnight to form homogeneous solution with concentration of 40 mg mL−1 before use. ITO-coated glass slides were cleaned with ultrasonic successively in chloroform and ethanol for 10 minutes. The PProDOT solution was then spin coated on ITO-coated glass slides with a spin speed of 800 rpm and 600 rpm to generate films of thicknesses of ~500 nm and ~1000 nm, respectively.
Surface modification of ITO
For surface roughening, two modification methods were employed to increase the roughness of ITO surface. In the first method, the ITO was ground by P1200 Starcke silicon carbide sandpaper. Very gentle force was applied in two orthogonal directions in sequence to generate visible clouds on ITO surface. The ground ITO was then cleaned through the processes described in the film processing part. A second method of modification involves the coating of SiO2 nanoparticles after cleaning. Monodisperse SiO2 nanoparticles with the diameter around 200 nm were synthesized by Stöber method56 and then were dispersed in EtOH by sonication to form homogenous solution with concentration of 0.13 g mL−1. The solution was then spin coated on the pre-cleaned ITO/glass with spin speed of 1500 rpm. After being put in the 90 °C oven for a few minutes, the EtOH volatized completely, which produced a solid SiO2 film on the ITO/glass substrate. The control experiment was done using as-received ITO after the same cleaning procedure.
Electrochemistry test
To allow indentation on the thin film, a half-cell configuration was used. The PProDOT film on ITO, a Pt wire, and a homemade Ag/AgCl wire57 were used as the working electrode, counter electrode, and reference electrode, respectively. 1 M LiPF6 in propylene carbonate (PC, Sigma Aldrich) was used as the electrolyte. All the electrochemistry experiments were done at the Versa Stat 3 potential station. For indentation test and scratch test on oxidized films, a voltage of 1 V against the reference electrode was applied. For the durability test, a three-electrode cell was fabricated for the cyclic test with 0.2 M LiTFISI in PC as the electrolyte. Voltammetry experiments were performed between 1.2 V and −0.2 V with a scan rate of 40 mV/s. The charge density was calculated by the equation \({\int} {\frac{{j{\rm{d}}V}}{s}}\), where the charge density has the unit of mC cm−2, j is the current density (mA cm−2), s is the scan rate (V s−1), and V is the voltage (V).
Targetted indentation and scratch tests
Instrumented nanoindentation (G200 Nano-indenter, KLA) was implemented to probe the mechanical properties of the films. All tests were done in an Ar filled glovebox to eliminate the chemical degradation by moisture and oxygen. During the test, load–displacement curve was recorded, from which modulus and hardness were calculated. The thin film method was used to calculate modulus, as implemented in the NanoSuite software45. To measure the thickness of the films, the raw displacement method and scratch test were used. For both methods, the indenter tip approaches the film until the surface is found. The recorded raw displacement at detected surface unveils the thickness of the film (Fig. 2a). Detailed explanation can be found in the Results section. The AFM (Veeco Multimode) data for comparison was processed via an online tool at https://www.profilmonline.com/.
To explore the degradation mechanism during the cyclic redox reactions, FEA was implemented using COMSOL Multiphysics TM (COMSOL Multiphysics 5.3, Sweden). A soft, compliant thin film (thickness of 500 nm, width of 10 um) is on a hard, stiff substrate. Elastic and perfectly plastic relationship was assumed for the polymer film. The modulus, 809 MPa, was measured from the indentation test. The yield stress, 23.2 MPa, was estimated to be 1/3 of the hardness58. The substrate deforms elastically with a modulus of 80 GPa. The interface debonding was simulated by the cohesive zone model59. Maximum normal (shear) strength was set as σγ (σγ/\(\sqrt 6\)) such that the interfacial opening crack (sliding) occured upon yielding of the film. Interfacial fracture toughness was estimated to be 1 J m−2 for both mode I and mode II cracks60. Analogous to the thermal expansion, an isotropic strain of 10% was applied to the film upon oxidation and then reduced to 0 during reduction. The effect of the mesh size was tested and convergence of results was obtained.
Serpe, M. J. Fine-tuned gel particles enable smart windows for energy efficiency. Nature 565, 438 (2019).
Granqvist, C.-G. Out of a niche. Nat. Mater. 5, 89 (2006).
Shin, H. et al. Energy saving electrochromic windows from bistable low-HOMO level conjugated polymers. Energy Environ. Sci. 9, 117–122 (2016).
He, J. et al. Highly transparent crosslinkable radical copolymer thin film as the ion storage layer in organic electrochromic devices. ACS Appl. Mater. Interfaces 10, 18956–18963 (2018).
Krebs, F. C. Electrochromic displays: the new black. Nat. Mater. 7, 766–767 (2008).
Beaujuge, P. M., Ellinger, S. & Reynolds, J. R. The donor–acceptor approach allows a black-to-transmissive switching polymeric electrochrome. Nat. Mater. 7, 795–799 (2008).
Grätzel, M. Ultrafast colour displays. Nature 409, 575 (2001).
Brooke, R. et al. Greyscale and paper electrochromic polymer displays by UV patterning. Polymers 11, 267 (2019).
Beaujuge, P. M. & Reynolds, J. R. Color control in π-conjugated organic polymers for use in electrochromic devices. Chem. Rev. 110, 268–320 (2010).
Zhang, Y.-M. et al. A single-molecule multicolor electrochromic device generated through medium engineering. Light.: Sci. Appl. 4, e249 (2015).
Amb, C. M., Dyer, A. L. & Reynolds, J. R. Navigating the color palette of solution-processable electrochromic polymers. Chem. Mater. 23, 397–415 (2011).
Jensen, J. & Krebs, F. C. From the bottom up–flexible solid state electrochromic devices. Adv. Mater. 26, 7231–7234 (2014).
Heinze, J., Frontana-Uribe, B. A. & Ludwigs, S. Electrochemistry of conducting polymers—persistent models and new concepts. Chem. Rev. 110, 4724–4771 (2010).
Savva, A. et al. Influence of water on the performance of organic electrochemical transistors. Chem. Mater. 31, 927–937 (2019).
Wang, S., Li, F., Easley, A. D. & Lutkenhaus, J. L. Real-time insight into the doping mechanism of redox-active organic radical polymers. Nat. Mater. 18, 69 (2019).
Otero, T. F. & Boyano, I. Comparative study of conducting polymers by the ESCR model. J. Phys. Chem. B 107, 6730–6738 (2003).
Wei, B., Liu, J., Ouyang, L., Kuo, C.-C. & Martin, D. C. Significant enhancement of PEDOT thin film adhesion to inorganic solid substrates with EDOT-acid. ACS Appl. Mater. Interfaces 7, 15388–15394 (2015).
Momodu, D. Y., Tong, T., Zebaze Kana, M. G., Chioh, A. V. & Soboyejo, W. O. Adhesion and degradation of organic and hybrid organic-inorganic light-emitting devices. J. Appl. Phys. 115, 084504 (2014).
Otley, M. T. et al. Acrylated poly(3,4-propylenedioxythiophene) for enhancement of lifetime and optical properties for single-layer electrochromic devices. ACS Appl. Mater. Interfaces 6, 1734–1739 (2014).
Xu, R. et al. Heterogeneous damage in Li-ion batteries: experimental analysis and theoretical modeling. J. Mech. Phys. Solids 129, 160–183 (2019).
Shpigel, N. et al. In situ hydrodynamic spectroscopy for structure characterization of porous energy storage electrodes. Nat. Mater. 15, 570–575 (2016).
Poornesh, K. K., Xiao, Y. & Cho, C. Thermo-mechanical response of fuel cell electrodes: constitutive model and application in studying the structural response of polymer electrolyte fuel cell. Fuel Cells 13, 217–226 (2013).
Bay, L., West, K., Sommer-Larsen, P., Skaarup, S. & Benslimane, M. A conducting polymer artificial muscle with 12% linear strain. Adv. Mater. 15, 310–313 (2003).
Smela, E. & Gadegaard, N. Surprising volume change in PPy(DBS): an atomic force microscopy study. Adv. Mater. 11, 953–957 (1999).
Pei, Q. & Inganaes, O. Electrochemical applications of the bending beam method. 1. Mass transport and volume changes in polypyrrole during redox. J. Phys. Chem. 96, 10507–10514 (1992).
Della Santa, A., De Rossi, D. & Mazzoldi, A. Performance and work capacity of a polypyrrole conducting polymer linear actuator. Synth. Met. 90, 93–100 (1997).
Collins, L., Liu, Y., Ovchinnikova, O. S. & Proksch, R. Quantitative electromechanical atomic force microscopy. ACS Nano, https://doi.org/10.1021/acsnano.9b02883 (2019).
Ispas, A., Peipmann, R., Bund, A. & Efimov, I. On the p-doping of PEDOT layers in various ionic liquids studied by EQCM and acoustic impedance. Electrochim. Acta 54, 4668–4675 (2009).
Ispas, A., Peipmann, R., Adolphi, B., Efimov, I. & Bund, A. Electrodeposition of pristine and composite poly(3,4-ethylenedioxythiophene) layers studied by electro-acoustic impedance measurements. Electrochim. Acta 56, 3500–3506 (2011).
Schoetz, T. et al. Understanding the charge storage mechanism of conductive polymers as hybrid battery-capacitor materials in ionic liquids by in situ atomic force microscopy and electrochemical quartz crystal microbalance studies. J. Mater. Chem. A 6, 17787–17799 (2018).
Ouyang, L. et al. Poly[3,4-ethylene dioxythiophene (EDOT)-co-1,3,5-tri[2-(3,4-ethylene dioxythienyl)]-benzene (EPh)] copolymers (PEDOT-co-EPh): optical, electrochemical and mechanical properties. J. Mater. Chem. B 3, 5010–5020 (2015).
Qu, J., Ouyang, L., Kuo, C. & Martin, D. C. Stiffness, strength and adhesion characterization of electrochemically deposited conjugated polymer films. Acta Biomater. 31, 114–121 (2016).
Lyutov, V., Gruia, V., Efimov, I., Bund, A. & Tsakova, V. An acoustic impedance study of PEDOT layers obtained in aqueous solution. Electrochim. Acta 190, 285–293 (2016).
Sen, S. et al. In situ measurement of voltage-induced stress in conducting polymers with redox-active dopants. ACS Appl. Mater. Interfaces 8, 24168–24176 (2016).
He, J., You, L. & Mei, J. Self-bleaching behaviors in black-to-transmissive electrochromic polymer thin films. ACS Appl. Mater. Interfaces 9, 34122–34130 (2017).
Guan, S., Elmezayyen, A. S., Zhang, F., Zheng, J. & Xu, C. Deterioration mechanism of electrochromic poly(3,4-(2,2-dimethylpropylenedioxy)thiophene) thin films. J. Mater. Chem. C. 4, 4584–4591 (2016).
He, J., You, L., Tran, D. T. & Mei, J. Low-temperature thermally annealed niobium oxide thin films as a minimally color changing ion storage layer in solution-processed polymer electrochromic devices. ACS Appl. Mater. Interfaces 11, 4169–4177 (2019).
Shen, D. E., M. Österholm, A. & R. Reynolds, J. Out of sight but not out of mind: the role of counter electrodes in polymer-based solid-state electrochromic devices. J. Mater. Chem. C. 3, 9715–9725 (2015).
Ouyang, L. et al. Enhanced PEDOT adhesion on solid substrates with electrografted P(EDOT-NH2). Sci. Adv. 3, e1600448 (2017).
Villemin, E. et al. Improved adhesion of poly(3,4-ethylenedioxythiophene) (PEDOT) thin film to solid substrates using electrografted promoters and application to efficient nanoplasmonic devices. Synth. Met. 248, 45–52 (2019).
Vasconcelos, L. S., Xu, R. & Zhao, K. Operando nanoindentation: a new platform to measure the mechanical properties of electrodes during electrochemical reactions. J. Electrochem. Soc. 164, A3840–A3847 (2017).
Ashby, M. F. & Jones, D. R. H. in Engineering Materials 1 4th edn. (eds Ashby, M. F. & Jones, D. R. H.) 115–133 (Butterworth-Heinemann, 2012). https://doi.org/10.1016/B978-0-08-096665-6.00008-8
Kausch, H. H. & Plummer, C. J. G. The role of individual chains in polymer deformation. Polymer 35, 3848–3857 (1994).
McCrum, N. G., Buckley, C. P. & Bucknall, C. B. Principles of Polymer Engineering (Oxford University Press, 1997).
Hay, J. & Crawford, B. Measuring substrate-independent modulus of thin films. J. Mater. Res. 26, 727–738 (2011).
Zhang, T.-Y. & Xu, W.-H. Surface effects on nanoindentation. J. Mater. Res. 17, 1715–1720 (2002).
Nix, W. D. & Gao, H. Indentation size effects in crystalline materials: a law for strain gradient plasticity. J. Mech. Phys. Solids 46, 411–425
Bentoumi, M. et al. Nano-indentation for probing mechanical properties of nanocomposites based on ethylene butyl acrylate copolymer and carbon black. J. Appl. Polym. Sci. 136, 47897 (2019).
Piro, B. et al. Fabrication and use of organic electrochemical transistors for sensing of metabolites in aqueous media. Appl. Sci. 8, 928 (2018).
Zhao, K., Pharr, M., Vlassak, J. J. & Suo, Z. Inelastic hosts as electrodes for high-capacity lithium-ion batteries. J. Appl. Phys. 109, 016110 (2011).
Hutchinson, J. W. & Suo, Z. in Advances in Applied Mechanics Vol. 29 (eds Hutchinson, J. W. & Wu, T. Y.) 63–191 (Elsevier, 1991).
Hillman, A. R., Daisley, S. J. & Bruckenstein, S. Ion and solvent transfers and trapping phenomena during n-doping of PEDOT films. Electrochim. Acta 53, 3763–3771 (2008).
Lane, M. Interface fracture. Annu. Rev. Mater. Res. 33, 29–54 (2003).
Ebert, D. & Bhushan, B. Transparent, superhydrophobic, and wear-resistant coatings on glass and polymer substrates using SiO2, ZnO, and ITO nanoparticles | Langmuir. Langmuir 28, 11391–11399 (2012).
Estrada, L. A., Deininger, J. J., Kamenov, G. D. & Reynolds, J. R. Direct (Hetero)arylation polymerization: an effective route to 3,4-propylenedioxythiophene-based polymers with low residual metal content. ACS Macro Lett. 2, 869–873 (2013).
Stöber, Werner, Fink, Arthur & Bohn, Ernst "Controlled growth of monodisperse silica spheres in the micron size range.". J. Colloid Interf. Sci. 26.1, 62–69 (1968).
da Silva, E. T. S. G., Miserere, S., Kubota, L. T. & Merkoçi, A. Simple on-plastic/paper inkjet-printed solid-state Ag/AgCl pseudoreference electrode. Anal. Chem. 86, 10531–10534 (2014).
Ashby, M. F. & Jones, D. R. H. in Engineering Materials 1 4th edn. (eds. Ashby, M. F. & Jones, D. R. H.) 157–170 (Butterworth-Heinemann, 2012). https://doi.org/10.1016/B978-0-08-096665-6.00011-8
de Castro, Pmst, Marques, At, de Moura, Mfsf & Gonçalves, Jpm Interface element including point‐to‐surface constraints for three-dimensional problems with damage propagation. Eng. Comput. 17, 28–47 (2000).
Hohlfelder, R. J., Luo, H., Vlassak, J. J., Chidsey, C. E. D. & Nix, W. D. Measuring interfacial fracture toughness with the blister test. MRS Proc. 436, https://doi.org/10.1557/PROC-436-115 (1996).
K. Z. acknowledges the support by the National Science Foundation through the grant CMMI-1726392. J. M. is grateful for the support from Ambilight Inc.
School of Mechanical Engineering, Purdue University, West Lafayette, IN, 47907, USA
Xiaokang Wang
, Luize Scalco de Vasconcelos
, Yung C. Shin
& Kejie Zhao
Department of Chemistry, Purdue University, West Lafayette, IN, 47907, USA
Ke Chen
, Jiazhi He
& Jianguo Mei
Search for Xiaokang Wang in:
Search for Ke Chen in:
Search for Luize Scalco de Vasconcelos in:
Search for Jiazhi He in:
Search for Yung C. Shin in:
Search for Jianguo Mei in:
Search for Kejie Zhao in:
X. W., K. Z. and J. M. conceived the idea and designed the in situ experiments. X. W. and L. V. performed the in situ measurements. X. W. performed the finite element analysis. K. C. and H. J. performed the interfacial modification of the electrode and the electrochemistry characterization. X. W. conducted optical profilometer measurement under the guidance of Y. S. All authors contributed in writing the paper.
Correspondence to Jianguo Mei or Kejie Zhao.
Peer review information Nature Communications thanks Luca Beverina and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Peer reviewer reports are available.
Peer Review File
Description of Additional Supplementary Files
Supplementary Movie 1
Wang, X., Chen, K., de Vasconcelos, L.S. et al. Mechanical breathing in organic electrochromics. Nat Commun 11, 211 (2020). https://doi.org/10.1038/s41467-019-14047-8
Nature Communications menu
Editors' Highlights

redpajama_set_name: RedPajamaCommonCrawl


text:
Culver Little League 10-11 Year Olds Set to Start Tournament
Culver City's finest 10 and 11-year-old baseball players will be in action on Friday, June 26 at 5 pm against perennial powerhouse West Los Angeles in the Little League District 25 All Star Tournament opener.
The Culver City All Stars have been hard at work under the tutelage of Culver City High and USC graduate Chip Netzel, who has successfully guided numerous Culver City All Star teams and has come out of retirement to work with this special group of players.
The All Stars include four returning two-three time all stars (Andy Perez, Brandon Zeidman, Diego Lopez and Travers Tobis), an additional seven returning all stars from last season (Jared Bojorquez, Jesse Tanahara, Leo Matsuoka, Oliver Frye, Stephan Thomas, Thomas Chee, and Tommy Peacock) and four first-time all stars (Devin Hayden, Elijah Adams, Kekoa Check, and Martin Lucero).
In addition to Netzel the team is coached by Andrew Thomas, Brandy Peacock, Henry Brandon, Rob Peacock and Scott Zeidman. Past and present members of the Culver City High Varsity Baseball and Softball teams, including Daniel Hennessey, Michael Netzel, Ava Fairbanks, Jason Zeidman, Mason Mulvihill, Christian De Los Santos have been instrumental at practices as well.
The tournament begins on June 26 and continues through July 11. All games are at North Venice Little League, located at 3321 Grandview Boulevard, Los Angeles. Admission is free.


text:
Alphonse Wilson verbosifyin' here, once again. Need to talk a bit 'bout names. Some of you might know me by my nickelname, Windy.
One Man's Perspective: Christmas can be tough for many
While we need to be of a celebratory spirit during the Christmas season — it is about the savior of mankind after all, despite mass marketing to the contrary — it is also important to remember those around who struggle during the holiday season as it brings cause to reflect on loss.
Letter to the Editor: Gifted and gullible, the gift of humor
• I suspect the memoir below is not exactly a letter to editor; however, it may be timely with the recent blizzard.
Letter to the Editor: 'It's a Wonderful Life'
I had the opportunity to attend a performance of "It's a Wonderful Life: A Live Radio Play" at Arts on Grand, which was presented by students from Nebraska Wesleyan University, including locals Natalie Kroll and Kyle Goeken. The show was just amazing and the performances were awesome. It was so heart-warming to see young people who have such talent and passion for doing something positive for the community during their time off from school.
Pastor's Column: It's Christmas, again!
Years ago, who can know how many, it would have been obvious that the celebration of Christmas was the birth of Jesus Christ, God in human flesh, Deity become humanity, Savior of all mankind (Emmanuel).
Dud was awfully quiet all through the daily dissemination of anything on page one of the Valley Weekly Miracle, which wasn't like him at all. Just sucked down caffeine and silently shook his head now and then.
"Anita OK, Dud?"
"Oh … sure, Doc."
"You OK?"
He nodded, then looked up with a wistful, philosophical look that our guys don't usually get until after the buttered toast. "Sometimes," he said, "I think it's pearls before swine, that's all."
Outdoors: Fishing in 2023
As a new year enters, I find myself looking back, but also looking forward. Looking back helps me see what the future might look like, and often, what I look back at are things related to fishing. Sometimes, maybe too much of the time, we focus on things that aren't so good. That's OK.
Guest Commentary: Revenue Estimate Update
The Revenue Estimating Conference, or REC met this week to give a better outlook of the state's budget.
Guest Commentary: The tale of the toymaker
There once was a toymaker.
But he was more than a toymaker. Call him an engineer, an architect, a designer, if you will. He created many fantastic things. He settled down to making toys, not because he couldn't make other things, but because toys delighted him so. There were two special toys, fashioned like a boy and a girl that he designed with extra special care.
On the Side: You just never know ...
Dear Readers: The following is column written by a fellow named Bob Thompson, who was a teacher and coach in my hometown. It is reprinted with permission.
Here's the story about a young man who was engaged to be married. He was in love, and his life was infected with that special pride and that vibrant joy that is peculiar to lovers.
Extension Outreach: Iowa farmland values hit all-time high despite concerns about higher inflation, interest rates
AMES — One year after skyrocketing 29%, the average value of an acre of Iowa farmland jumped another 17%, or $1,660, to $11,411 per acre. The nominal value of an acre of farmland is again higher this year than at any point since Iowa State University began surveying values in 1941. When adjusting for inflation, the 2022 average value surpasses the previous inflation-adjusted record value set in 2013 for the first time.
The CommStock Report: What kind of inflation is this?
While there is consensus, even at the Fed, that they left the spigot of monetary stimulus wide open too long resulting in inflation, they did achieve their aim of restoring the economy from the COVID pandemic near collapse, avoiding that catastrophe. Most have forgotten about that now, with complaints over the problem presently being faced of inflation and what it will take to quell it.
One Man's Perspective: Christmas decorations 'controversial?' How about a Satan Club
Each year, as we approach Christmas, it seems as though some school district or city council, finds itself challenged as it attempts to celebrate the traditional Christmas with decorations and music.
No nativity in the town square. It might offend someone.
No Christmas concert — it's a holiday concert now.
No Christian decorations in the classroom, only symbols of the holiday's commercial aspects — Santas and big fir trees and gingerbread cookies.
Letter to the Editor: Downfall of FTX
The downfall of cryptocurrency company FTX and its cohort Alameda Research along with the $8 billion of customer funds that vanished in thin air is troubling.
The FTX CEO Sam Bankman-Fried is an American product, a MIT graduate graced with a favored background. He was raised by professionals, Stanford Law professors. He attended top mathematics camps for precocious children.
Letter to the Editor: The most wonderful time of the year
The sounds of Christmas are definitely in the air. There's the FM station in the SRG family playing strictly Christmas carols and songs daily. The beautiful and inspiring rendition of the Messiah, with its local and regional musicians and singers, was enjoyed by many in the friendly confines of Sacred Heart Catholic Church. Just this past weekend, members of Grace United Methodist Church graced the community by performing the Journey to Bethlehem.
Pastor's Column: Messy Christmas
Editor's Note: Loveall's "Messy Christmas" has been republished several times since it first ran in the Dickinson County News. The Spencer Reporter would like to share it with readers this year.


"On we swept," and passed many a shoal and reef, just perceptible by a change of colour upon the face of the water or a long treacherous ripple; to our right was the coast of Bahreyn [Bahrain], its sandy monotony broken here and there by some small and dingy village. Near nightfall we sighted the western corner of Katar [Qatar], called in many maps Bahran, but on what authority I hardly know; certainly no one here ever gives it that name. Now "Bahran" is simply the nominative of which "Bahreyn" is the genitive or objective case; and hence I suspect that our geographers may have been led astray by some grammatical misapprehension of a phrase. The coast of Katar before us looked rocky, but not high; it is very desolate-seeming; at intervals rise small watch-towers, much like those seen on different points of the Syrian shore, and ascribed by popular tradition to the Empress Helena, wife of [Constantius Chlorus, and mother of] Constantine the Great.
During the night we were startled from slumber by the grinding of our keel upon a reef, an event followed by so much confusion, shouting, and awkward unseamanship, that our getting off was more the work of lucky chance than of the crew. Next day we had to endure foul wind and drizzling rain with nothing to shelter us, while we slowly worked our way up under Ras Rekan [Ra's Rakan, Ras Rakhan], the northernmost cape of the Katar promontory; a somewhat bold headland girt with cliffs thirty or forty feet high; we were long in getting round it. I noticed a good-sized fort on the heights; it belongs to a village situated in a gorge close by, but I have forgotten the name [Al Zubarah or Az Zubarah].
By the morning of the 28th [of January, 1863] we had fairly rounded Rekan, and drove southwards before the gale for Bedaa' [Al Bida, which was later engulfed by Doha]. The line of coast was all along steep, but of inconsiderable height; five or six villages, the abodes of fishermen, intervene between the cape and Bedaa', opposite which we arrived towards evening. Ebn-Khamees went on shore to pay his compliments to the chief and prepare a lodging; but the hour was late, and I preferred remaining on board the night. Next morning my companion returned to fetch me, and we waded together across a wide sandy reach till we entered Bedaa', the principal town of Katar at the present day.
It is the miserable capital of a miserable province. To have an idea of Katar, my readers must figure to themselves miles on miles of low barren hills, bleak and sun-scorched, with hardly a single tree to vary their dry monotonous outline; below these a muddy beach extends for a quarter of a mile seawards in slimy quicksands, bordered by a rim of sludge and seaweed. If we look landwards beyond the hills, we see what by extreme courtesy may be called pasture land, dreary downs with twenty pebbles for every blade of grass; and over this melancholy ground scene, but few and far between, little clusters of wretched, most wretched, earth cottages and palmleaf huts, narrow, ugly, and low; these are the villages, or rather the "towns" (for so the inhabitants style them), of Katar.
Yet poor and naked as is the land, it has evidently something still poorer and nakeder behind it, something in short even more devoid of resources than the coast itself, and the inhabitants of which seek here by violence what they cannot find at home. For the villages of Katar are each and all carefully walled in, while the downs beyond are lined with towers, and here and there a castle "huge and square" makes with its little windows and narrow portals a display of strength hardly less, so it might seem, superfluous than the Tower of London in the nineteenth century. But these castles are in reality by no means superfluous, for Katar has wealth in plenty, and there are robbers against whom that wealth must be guarded.
Whence comes this wealth amid so much apparent poverty, and in what does it consist? What I have just described is, so to speak, nothing but the heaps of rubbish and the rubbishy miners' huts about the shaft's month; close by is the mine itself, a rich and never-failing store. This mine is no other than the sea, no less kindly a neighbour to the inhabitants of Katar than their dry land is a niggard host.
In this bay are tbe best, the most copious pearl-fisheries of the Persian Gulf, and in addition an abundance almost beyond belief of whatever other gifts the sea can offer or bring. It is from the sea accordingly, not from the land, that the natives of Katar subsist, and it is also mainly on the sea that they dwell, passing amid its waters the one half of the year in search of pearls, the other half in fishery or trade.
Hence their real homes are the countless boats which stud the placid pool, or stand drawn up in long black lines on the shore; while little care is taken to ornament their land houses, the abodes of their wives and children at most, and the unsightly strong-boxes of their gathered treasures.
"We are all from the highest to the lowest slaves of one master, Pearl," said to me one evening Mohammed-ebn-Thanee [Muhammad bin Thani, 1800—1878], chief of Bedaa'; nor was the expression out of place. All thought, all conversation, all employment, turns on that one subject; everything else is mere by-game, and below even secondary consideration.
I mentioned robbers and the danger of pillage. From each other, indeed, the men of Katar have, it seems, little to fear. Too busy to be warlike, they live in a passive harmony which almost dispenses with the ordinary machinery of government itself. Ebn-Thanee, the governor of Bedaa', is indeed generally acknowledged for head of the entire province, which is itself dependant on the Sultan of 'Oman; yet the Bedaa' resident has in matter of fact very little authority over the other villages, where everyone settles his affairs with his own local chief, and Ebn-Thanee is for those around only a sort of collector-in-chief, or general revenue-gatherer, whose occupation is to look after and to bring in the annual tribute on the pearl fishery [Qatar was controlled by Bahrain from the 1850s to 1868, and paid tribute to Bahrain until 1872].
Mohammed-el-Khaleefah [Muhammad ibn Khalifah Al Khalifa of Bahrain] has also a sort of control or presidential authority in Katar, but its only exercise in the hands of this worthy seems to be that of choosing now and then a pretty girl (for the female beauty of 'Oman extends itself, though in an inferior degree, to Katar), on whom to bestow the brief honours of matrimony for a fortnight or a month at furthest, with a retiring pension afterwards. While I was myself at Bedaa' the uxorious Khaleefah paid a visit to the neighbouring town of Dowhah, and there lightly espoused a fair sea-nymph of the place, to he no less lightly divorced long before my return from 'Oman. No solemnity was spared on the occasion; jurists were consulted, the dowry paid, public rejoicings were ordered, and public laughter came unbidden; while Mohammed wasted the hard-gained wealth of Menamah [Manamah, capital of Bahrain] and Moharrek [Al-Muharraq, 2nd largest city in Bahrain] in the pomp of open vice.
Zabarah, the largest of the island towns, indeed the only one of any territorial importance, is the residence of one of the El Khaleefahs ; but it does not therefore claim any particular preeminence over the remaining localities of the province.
But if the people of Katar have peace within, they are exposed on the land side to continual marauding inroads from their Bedouin neighbours, the Menaseer and Aal-Morrah [Al-Murrah]. The former of these tribes is numerous and warlike, and their favourite range of rapine or pasture extends from the frontiers of Hasa [Al-Hasa] to those of 'Oman proper near Sharjah. Few nomad clans give more annoyance to the inhabited districts, and few, if accounts be correct, have amassed a greater amount of ill-gotten opulence from plunder and bloodshed.
These marauders possess large droves of camels and flocks of sheep, acquired and augmented at the expense of the villagers; and from the barren desert hard by, their retreat when pressed by danger, they bring their animals to pasture on the narrow strip of upland that lies between the coast-hills and the Dahnii. Hence the necessity for the towers of refuge which line the uplands: they are small circular buildings from twenty-five to thirty feet in height, each with a door about half-way up the side and a rope hanging out; by this compendious ladder the Katar shepherds, when scared by a sudden attack, clamber up for safety into the interior of the tower, and once there draw in the rope after them, thus securing their own lives and persons at any rate, whatever may become of their cattle. For to scale a wall fifteen feet high is an exploit beyond the ingenuity of the most skilful Bedouin. At times the Menaseer, emboldened by impunity (for the people of Katar have no great pretensions to warlike valour), attack the main villages, and carry off more valuable booty than kine [cattle] and sheep. Hence the origin of the strongholds or keeps within the towns themselves, and of the walls which surround them.
Further down the coast towards the east begin the settlements of Benoo-Yass, an ill-famed clan, half Bedouins, half villagers, and all pirates; the very same whose cruisers have in former times given to this district the ominous name of "Pirate coast." The head point or main centre of Benoo-Yass is Soor; it is, so I was informed, a mere aggregation of huts, clustered under some old and ruined fortresses, dens of the robbers. The Benoo-Yass belong to the original inhabitants of 'Oman, and though devoid of its civilization, partake in its political and national feelings; hence they are not only haters of all Muslims and Wahhabees [Wahhabis], but even fierce enemies and aggressors whenever occasion permits.
When plunder is the order of the day, they readily join hands with the Menaseer, though widely different from them in origin and in appearance. For the Menaseer, judging by tradition, physical outline, and dialect, are a branch of the great 'Abs family [Banu Abs], of whom was the famous 'Antarah-ebn-Sheddad [Antarah ibn Shaddad], and are, accordingly, by race Nejdeans from Keys-'Eylan, while Benoo-Yass trace their origin to the Kahtanee [Qahtanite] family of Modhej, and travelled hither northwards from Hadramaut, so runs their tale.
Profit, however, like misery, may unite strange bedfellows. Both the Menaseer and Benoo-Yass have been much repressed of late by the activity of Ahmed-es-Sedeyree, the Nejdean resident at Bereymah [Dahiyah, Oman] (the same whose brother 'Abd-el-Mahsin-es-Sedeyree entertained us at Mejmaa'); while at sea the red 'Omanee pennon of the pirates has grown pale before the redder cross of St. George; and none but pearl-oysters and fishes have any violence to fear in this bight of the Persian Gulf at the present day.
Of the third great clan hereabouts, namely, Afd-Morrah, the tenants of the Dahna [Ad-Dahna Desert] itself, and still more numerous and widespread, though luckily less pugnacious, than the Menaseer, I have already made mention. The Bedouins of this tribe, who visit Katar and 'Oman, now for trade and now for plunder, do not acknowledge Wahhabee sovereignty, but are, after their irregular fashion, some of them tributaries to the Sultan of Oman, while some remain at the bidding and buying of subordinate land-chiefs.
The climate of Katar is remarkably dry; under the arid breath of the encroaching desert, the sea-air only a few miles inland seems to lose all trace of humidity. The soil is poor, gravel and marl mixed with sand; occasional springs of water supply wells laboriously pierced through the encrusted upper strata. The gardens are small and unproductive, nor did I see any cornfields or date-groves worthy of the name. The air too is said to be unhealthy; perhaps the rotting pools of stagnant sea-water that border all the coast, are the cause of this.
State of Qatar: Ruled by the Al Thani family since the mid-1800s, Qatar transformed itself from a poor British protectorate noted mainly for pearling into an independent state with significant oil and natural gas revenues.
During the late 1980s and early 1990s, the Qatari economy was crippled by a continuous siphoning off of petroleum revenues by the Amir [Khalifa bin Hamad Al Thani], who had ruled the country since 1972. His son, the current Amir HAMAD bin Khalifa Al-Thani, overthrew him in a bloodless coup in 1995.
In 2001, Qatar resolved its longstanding border disputes with both Bahrain and Saudi Arabia.
As of 2007, oil and natural gas revenues had enabled Qatar to attain the second-highest per capita income in the world.
Such is the general outline of Katar. On landing at Bedaa' we went right to the castle, a donjon-keep, with outhouses at its foot, offering more accommodation for goods than for men.
Under a mat-spread and mat-hung shed within the court sat the chief, Mohammed-ebn-Thanee, a shrewd wary old man, slightly corpulent, and renowned for prudence and good-humoured easiness of demeanour, but close-fisted and a hard customer at a bargain; altogether, he had much more the air of a businesslike avaricious pearl-merchant (and such he really is), than of an Arab ruler. Bound him were placed many sallow-featured individuals, their skins soddened by frequent sea-diving, and their faces wrinkled into computations and accounts. However, Ebn-Thanee, though eminently a "practical " man, had thus far put his sedentary habits to intellectual profit, that by dint of study he had rendered himself a tolerable proficient in literary and poetical knowledge, and took great pleasure in discussing topics of this nature. Nay, he even pretended to have some medical skill, and did I think really possess about the same amount of it that many an old woman may boast of in a country village of Lancashire or Essex. Besides, he liked a joke, and could give and take one with a good grace.
He enquired about my journey. I replied that I had no special business on hand for Katar, and that I was merely on my way to Mascat [Muscat, Oman] in search of herbs and drugs [Palgrave, a Jesuit priest who later renounced the church, was posing as a Syrian physician while gathering intelligence for the Jesuits and for the French Government of Napoleon III].
Ebn-Khamees, who was now an important character, thanks to the presents in his charge, sat close by the chief in all the grandeur of a new black mantle and a silken head-dress, furnished by Aboo-'Eysa. Mohammed-ebn-Thanee himself wore a Bengalee turban, of the date of Suraj-Dowlah [Siraj ud-Daulah, 1733-1757], to judge by its dingy appearance; his robe was an overdress which a Damascene grocer would have been ashamed to display out of doors.
He apologized for want of room to lodge us suitably in the palace itself. I cast a look round its narrow precincts and loopholed stone walls, and fully accepted the excuse. Ebn-Thanee had by anticipation caused a warehouse close by to be emptied of the dates it held, and fitted up in Katar style for our reception; that is, mats were spread, and nothing more. We of course expressed due thanks for hospitality here regarded as munificent, drank coffee, talked awhile, and retired.
Ebn-Khamees had soon shot his bolt, that is, offered his presents. But their receiver, the old pearl-monger, could not with equal speed make up his mind about the amount to be tendered in requital, and no less than eight days passed before a suitable retribution had been proposed and accepted. This delay, especially in bad lodgings and with much before us better worth seeing, was annoying enough, the more so that four days were fully sufficient for knowing all worth the knowing in so monotonous a country. However, the time did not go by wholly without profit, for it gave me leisure to make some excursions into the vicinity.
The town of Bedaa' itself was soon explored. It owns a long narrow and dirty market-place, where some Bahreyn shopkeepers and artisans ply their business on a small scale; for the rest, Bedaa' consists of a mass of little narrow dingy houses, separated by irregular lanes. The total amount of its inhabitants when on land, which is not often the case, reaches about six thousand; a few colonists from Hasa come hither to try their fortune and grumble at the country. Everywhere one meets fishermen's wives, and their brats, more dirty and more clamorous than any in Crabbe's [George Crabbe 1754—1832] "Borough," and ill-dressed men, too careworn to be sociable.
If we go down to the beach, we find there line on line of huge black boats, whose grooved edges show where the divers' cords have been let down, for a rope is always tied round the waist of the plunger, while the other end is held by his companions, and by this they draw him up when required.
And now my reader may fairly appreciate Bedaa', and the attractions it presents to eyes, ears, and, like most seaport towns, to nostrils also. Still the people are not by nature ungracious or inhospitable, but they are over-engrossed by their occupations; and lastly, long-continued diving, accompanied by all the privations and hardships inseparable from weeks and months at sea in open boats, give to the males the appearance of men totally knocked-up.
Till within quite recently Bedaa' owned neither mosque nor any other recognized place for public worship, and we must hope that every one satisfied his devotional obligations in private. But since the late Nejdean invasion, and the establishment of Ahmedes-Sedeyree at Bereymah, a "revival" in favour of Islam has taken place in some parts of Katar, and two mosques now adorn the town of Bedaa'. One of these edifices is large, but plain and unomamental, in the approved Wahhabee taste; it stands to the north of the castle. The other, situated at the opposite extremity of the village, is smaller, but much handsomer, with an open arched portico in semi-Persian style. Mohammed-ebn-Thanee, whether from political motives or from sincere conviction, I know not, perhaps from a mixture of both, is very devout, and often performs in person the duties of Imam in the larger mosque, for want of a more appropriate personage in this town, where few sacrifice to Minerva.
The smaller "Mesjid" [mosque] is destined for the use of his eldest son and heir Kasim [Jassim bin Muhammed Al Thani, 1826—1913], a more dashing character than his father, but equally close-fisted. His castle or residence, a white square building with little battlements and pointed windows, almost like imitation Gothic, stands near the southern extremity of Bedaa'; beyond it low rocks shut in the bay.
We were soon tired of drinking bad coffee, for the berry of Yemen here gives place to the inferior produce of India, unpalatable stuff to those accustomed to real Mokha [Mocha]; tired too of hearing or spinning long yarns in Ebn-Thanee's divan, and of snuffing up the bad air of a dirty coast and muddy beach. So we resolved to diversify our Katar existence by a few trips to the localities around.
My first visit was to Dowhah [Doha], a village to the north of Bedaa', and of about half its size; it is situated, as its name of "inlet " or "creek" imports, in a small deep bay, where the cliffs behind, sixty or eighty feet high, give it a somewhat picturesque appearance. But the houses of Dowhah are even lower and meaner than at Bedaa', and the market-place is narrower and dirtier. Two castles overtop the place: one stands on the neighbouring cliff, the other within the town itself; the chief is a small sub-collector to Ebn-Thanee. Hither, three days before my departure from Katar, arrived the wife-hunting governor of Bahreyn in pacific quest of a temporary Helen, as above described.
My next excursion was to Wokrah [Al Wakrah], a town equalling Bedaa' in extent, but situated higher up on the shore, and of a more cheerful character. Its young chief, also a Mohammed by name, but not of the Ebn-Thanee family, proved intelligent and polite, besides being much more hospitable than his namesake at Bedaa'. In government and police Wokrah is independent of any other town. Under the patronage of its chief, several small traders and artisans from Bahreyn have established themselves here; and Wokrah has on the whole a thriving look.
The road leading to it from Bedaa' is bleak and barren, close along the coast; the distance is within ten miles. I made the journey on a hired donkey, these animals being the ordinary conveyance in Katar for short distances; my beast was equipped with a sidesaddle, which made me look if not like a gentleman, at least in one respect like a lady, while my long Arab shirt might represent a riding-habit. Nor did I take with me any companion, so secure are the coast-roads, and so many the comers and goers in this land where business supersedes or suspends mischief.
But my associate Ebn-Khamees, more in search of profit than of pleasure, imagined that a few packages of dates might be acceptable to Kasim, the old chief's son, and would needs try his luck with that nobleman, in spite of all I could say to the contrary. Kasim was at the time absent from Bedaa' on a hawking-party some twelve or fourteen miles off to the southwest. We procured dromedaries, mounted, and rode on our way, over desert uplands and pebbly tracts. We passed bands of women in quest of water from the distant wells; and flocks of sheep, or rather of goats, for the breed is of ambiguous appearance, well guarded by numerous shepherds; occasionally we met some traveller with his lance over his shoulder against the perils of a Bedouin frontier. No trees, little herbage, and a cold keen wind from the north.
At last we reached the desired spot, a tolerably grassy valley amid undulations and hillocks on the marge of the "waste and howling wilderness." Here in tents, bivouac guise, was the young chief with his retainers, on the look-out for partridges and quails, of which he had hitherto caught few; with an eye too on hares, or I had better said on those equivocal animals, half hare, half rabbit, which abound on the Arab mainland. Kasim had with him about twenty horsemen, falconers, and half a dozen lovely hawks, besides two brace of greyhounds ("Selakee" they call them here); a thorough hunting-party, except that there was not a single fowling-piece among them.
We remained half a day in his highness's society, and enjoyed a sort of Arab pic-nic, enlivened by hawking. For a minute description of this sport in the East, I may refer my readers to that well-known and accurate work, Layard's [Sir Austen Henry Layard, 1817–1894] "Nineveh..."
Yoosef-ebn-Khamees delivered his presents and received fair words, but little else. Kasim appeared to me even less amiable than his father; narrow-minded and less well informed than the old man, while at the same time he was more pretentious and haughty. He affects the Nejdean in dress and manner, but has far more devotion at heart for the diva pecunia than for the precepts of the Coran [Qur'an, Koran]. His men, like those of Justice Shallow [from Shakespeare's The Merry Wives of Windsor], had a "semblable coherence with their master's spirits," which rendered their society dry and unprofitable.
Next morning we took leave of Kasim, and returned by the way we came, to eat fish and drink bad coffee with Ebn-Thanee. We waited yet a couple of days, hoping for a favourable wind to convey us straight across the Gulf to 'Oman. The land journey by the coast would have required at least a fortnight, perhaps more; and the reports current in Katar touching the rapacity of the Benoo-Yass, their treachery and other ill qualities, did not encourage us to try their hospitality, especially with Yoosef's presents and retributions in our keeping. Besides, all affirmed the road to be even more desolate and monotonous than that of Katar itself, and that it could offer nothing to repay our labour in traversing it. The sands of the Dahna reach the very margin of the sea; a glance at the map will enable my reader to understand this district.
Accordingly we proposed following the diameter of the semicircle over-sea, in preference to its sandy circumference, and thus make direct for Sharjah, the first considerable town situated within the territory of 'Oman proper. For this a worthy young sea-captain, native of Charak [Bandar Charak] on the opposite Persian coast, offered us his ship and services. But here again the future had for us more roundabouts in store than had entered into our original calculation. "The traveller can reckon his setting out, not his return," says a trite Arab proverb, true in some degree everywhere, but most so in the East.
Our captain was soon ready for sailing, and his crew on board. We made our parting arrangements, and on February 6 , while a lovely evening promised a fair morrow, and a light west wind seemed to ensure us a good and speedy passage to Sharjah, we took our leave of Mohammed-ebn-Thanee, who had now become very intimate in his way, said adieu to three or four other friends acquired at Bedaa', and entrusted ourselves to a little boat, wherein Faris, to give our captain his proper name, with his younger brother Ahmed and two of the crew, had come to fetch us off to the ship. We now crossed by rowing the same space that I had footed over the sand some days before; but then it had been ebb, whereas now the full tide was running in ten or twelve feet deep.
The flux and reflux of the waters is here only once in twenty-three hours, that is, at every alternate period; at Bahreyn and on the coasts of Persia and 'Oman it is once in eleven. The peculiar position of Katar and of the Benoo-Yass region at the bottom of a deep gulf, will explain this meteorological phenomenon to my scientific readers; the Arabs content themselves with noticing and wondering at it.


text:
module Paynl
  class Config
    @@apiToken=''
    @@tokenCode=''
    @@serviceId=''
    @@apiBase='https://rest-api.pay.nl'
    @@apiVersion=5

    # getTokenCode - Retrieves Pay.nl tokencode
    def self.getTokenCode
      return @@tokenCode
    end

    # setTokenCode - Sets Pay.nl tokencode
    def self.setTokenCode(tokenCode)
      @@tokenCode = tokenCode
    end

    # getApiToken - Retrieves Pay.nl api token
    def self.getApiToken
      return @@apiToken
    end

    # setApiToken - Sets Pay.nl api token
    def self.setApiToken(apiToken)
      @@apiToken = apiToken
    end

    # getServiceId - Retrieves Pay.nl Service Id
    def self.getServiceId
      return @@serviceId
    end

    # setServiceId - Set the Pay.nl Service Id
    def self.setServiceId(serviceId)
      @@serviceId = serviceId
    end

    # getApiVersion - Retrieves Pay.nl Api version
    def self.getApiVersion
      return @@apiVersion
    end

    # setApiVersion - Set the Pay.nl Api version
    def self.setApiVersion(apiVersion)
      @@apiVersion = apiVersion
    end

    # getApiUrl - Get constructed API Url for the given endpoint
    def self.getApiUrl(endpoint, version = nil)
      unless !version.nil?
        version = @@apiVersion
      end

      return @@apiBase + '/v' + version.to_s + '/' + endpoint + '/json'
    end
  end
end

redpajama_set_name: RedPajamaGithub