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WO2011036433A1 - Concentration de particules dans un écoulement de liquide - Google Patents

Concentration de particules dans un écoulement de liquide Download PDF

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Publication number
WO2011036433A1
WO2011036433A1 PCT/GB2010/001751 GB2010001751W WO2011036433A1 WO 2011036433 A1 WO2011036433 A1 WO 2011036433A1 GB 2010001751 W GB2010001751 W GB 2010001751W WO 2011036433 A1 WO2011036433 A1 WO 2011036433A1
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WO
WIPO (PCT)
Prior art keywords
flow
electrodes
liquid flow
laminar
particles
Prior art date
Application number
PCT/GB2010/001751
Other languages
English (en)
Inventor
Kai Friedrich Hoettges
Michael Pycraft Hughes
Original Assignee
The Secretary Of State For Defence
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Secretary Of State For Defence filed Critical The Secretary Of State For Defence
Publication of WO2011036433A1 publication Critical patent/WO2011036433A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C5/00—Separating dispersed particles from liquids by electrostatic effect
    • B03C5/02—Separators
    • B03C5/022—Non-uniform field separators

Definitions

  • the present invention is generally concerned with apparatus for concentrating and collecting particles in a particle suspension flow, and particularly apparatus comprising a planar interdigiialed electrode pair capable of inducing electro-osmotic vortices to alter the direction of particles in the flow and facilitate collection of a concentrated particle suspension.
  • Concentrating particles in a liquid flow has particular applicability to the fields of detection and identification of particles, and especially in systems whereby a detection means (such as a surface plasmon resonance biosensor) is in liquid How communication with the particle concentration means.
  • a detection means such as a surface plasmon resonance biosensor
  • Manipulation of particles in a liquid flow by dielectrophoresis is however inefficient due to the shallow depth of penetration of the dieleclrophoretic field.
  • a requirement thus exists for identifying alternative means for concentrating particles in a liquid low. Induced electro-osmotic flow, which is movement of a liquid between an electrode pair induced by applying an alternating potential to the electrode pair, is an alternative phenomenon to dieleclrophoresis for moving particles in a liquid.
  • Movement of the l iquid is driven by a combination of the alternating potential and a diffuse double layer of charge present at each electrode surface, with electro-osmotic vortices originating in the gap between the electrodes.
  • alternating potential a diffuse double layer of charge present at each electrode surface
  • electro-osmotic vortices originating in the gap between the electrodes.
  • the present invention generally aims to provide apparatus utilising induced electro- osmotic flow to manipulate particles in a l iquid flow, and especially to provide apparatus for concentrating and collecting particles in a particle suspension flow.
  • the present inveniion particularly aims lo provide apparatus capable of manipulating and concentrating particles within a continuous liquid flow, without removing the particles from the liquid flow.
  • Such an apparatus may have utilisation in a system wherein a detection means is in liquid communication with the apparatus, enabling a continuous flow of liquid through the apparatus to the detection means, and thus delivering a concentrated suspension of particles to the detection means.
  • the present invention provides apparatus for concentrating particles in a particle suspension How and collecting the resulting concentrated particle suspension comprising a liquid flow chamber defining a l iquid inlet and a liquid outlet arranged so as to provide laminar liquid flow therebetween, a pair of parallel planar electrodes separated by a gap of predetermined distance arranged in the liquid How chamber to contact the laminar liquid flow, and means for applying an alternating potential di fference to the electrode pair such to induce an electro-osmotic vortex in the laminar liquid How.
  • liquid outlet comprises a first and second outlet port and the electrode elements are aligned at an angle to the direction of laminar liquid (low such that the induced electro-osmotic vortex drives the particles in the particle suspension flow out of the direction of laminar liquid flow and towards the first outlet port facilitating collection of the concentrated particle suspension at the first outlet port.
  • the apparatus is capable of recovering a high concentration of particles at the first outlet port, and consequentially a low concentration of particles, or clear liquid, at the second outlet port, whilst providing a continuous flow.
  • the apparatus comprises multiple pairs of parallel planar electrodes arranged parallel with respect to each other. Multiple pairs of electrodes provide a plurality of gaps, and thus an apparatus capable of providing a plurality of electro-osmotic vortices. Since the pairs of electrodes are parallel and aligned the plurality of electro-osmotic vorlices will drive panicles to a greater extent out of the direction of laminar flow, and moreover the particles will be driven out of the direction of laminar flow in substantially the same manner. This movement of particles results in concentration of the particles within the liquid flow.
  • the multiple pairs of parallel planar electrodes may in particular be provided by an interdigitated electrode pair. The parallel planar electrodes would in this embodiment correspond to the interconnected digits of the interdigitated electrode pair.
  • an interdigitated electrode pair has a periodic pattern of interconnected paral lel in-plane digit-like or finger-like electrode elements, otherwise known as interconnected digits.
  • Interdigitated electrodes are commonly used electrode configurations. They have also been described as interconnected comb-l ike electrodes.
  • the multiple pairs of parallel planar electrodes are separated by the gap of predetermined distance.
  • Each electrode being separated from its neighbouring electrodes by the same distance provides an apparatus capable of providing electro-osmotic vortices of substantially uni form magnitude throughout the flow chamber.
  • the electrodes are preferably aligned at a single angle to the direction of laminar liquid flow, which may be provided by the electrodes being linear. Such an arrangement will provide electro-osmotic vortices that drive the particles out of the direction of laminar liquid (low in substantially the same direction (e.g. towards the same wall of a liquid flow chamber). Linear electrode elements provide better control of the particle movement, especially the direction of movement, and thereby concentration of the particles.
  • the electrodes may be displayed on one face of the flow chamber, and are preferably at, on or adjacent the base of the flow chamber.
  • the electrodes are preferably substantially arranged throughout the length and width of the flow chamber such that the majority, if not the entirety, of the laminar liquid (low may be affected by electro- osmotic vortices. Such an arrangement throughout the flow chamber will provide efficient movement and concentration of the panicles.
  • the electrodes are preferably not aligned in a direction perpendicular to the direction of the laminar liquid flow, and are preferably arranged such that the electrodes align in a direction between about 5° and 85° from the direction of the laminar How, more preferabl y between about 5° and 25°, such as 8°, 1 2°, 1 6°, 20° and 24°, and most preferably about 16°.
  • better efficiency of concentration is provided by shallower angles to the direction of laminar How, possibly as a particle wil l encounter more vortices, originating at each gap between electrodes, on its journey from the bulk laminar How towards the first outlet port if a shallower angle is used.
  • the predetermined distance of the gap between the electrodes is a distance suitable for providing an electro-osmotic vortex.
  • the distance of the gap influences the magnitude of the electric field across the gap, and thereby influences the magnitude of the vortex at a given voltage.
  • a distance of between about 50 ⁇ ⁇ to 200 ⁇ has been shown to be particularly effective in the apparatus of the first aspect, with an optimum gap of about 100 ⁇ .
  • the depth of the flow chamber should preferably be more than a distance equivalent to half the width of the electrodes to accommodate and utilise fully the induced electro-osmotic vortices.
  • the depth of the flow chamber should preferably be a distance less than about five times, and more preferably a distance less than about double, the width of the electrodes to fully utilise the effect of the electro-osmotic vortices to drive the particles.
  • Electrodes with a width of 200 ⁇ . ⁇ ⁇ perform particularly well in a flow chamber of depth 175 ⁇ .
  • the width of the electrodes is preferably between about 50 ⁇ and 600 ⁇ , more preferably between 100 to 300 ⁇ , and most preferably 200 ⁇ .
  • an interdigitated electrode pair providing linear electrodes (digits) of width 200 ⁇ , with a gap of 100 ⁇ , and aligned at an angle of 1 ° to the direction of laminar liquid flow. This was achieved in a flow chamber of depth 175 ⁇ or 300 ⁇ , and with a flow rale of laminar liquid flow of either 4. 1 or 6.2 ⁇ /min.
  • the flow rate of the laminar liquid flow is preferably between 4 ⁇ /min and 25 ⁇ /min, and more preferably between 4 ⁇ /min and 7 ⁇ /min.
  • the apparatus preferably further comprises a pump system connected to the l iquid inlet and both first and second outlet port of the l iquid outlet of the flow chamber to control the flow rate of the laminar liquid flow.
  • the pump system comprises pumps as known in the art, and preferably one pump controlling the flow rate at the inlet, and a pump at each outlet port externally stabilising the flow rate at both outlets, enabling production of a reproducible spl it, thus avoiding widely fluctuating flow ratios between the two outlets.
  • the apparatus of the first aspect is preferably for concentrating and collecting biological particles, such as spores, cells and viruses.
  • the present invention provides use of an apparatus comprising a liquid flow chamber arranged so as to provide laminar liquid flow, a pair of parallel planar electrodes separated by a gap of predetermined distance arranged in the l iquid flow chamber to contact the laminar liquid flow, and means for applying an alternating potential difference to the electrode pair, wherein the electrodes are aligned at an angle to the direction of laminar liquid flow such to induce an electro- osmotic vortex in the laminar liquid flow for concentrating particles in a particle suspension flow, and optionally collecting the resulting concentrated particle suspension.
  • the present invention provides use of electro-osmotic How for concentrating particles in a suspension flow, and optional ly collecting a resulting concentrated particle suspension.
  • Figure 1 is a schematic of electrode digits 1 angled to the plane of direction of laminar flow 2, the vortices 3 produced in the flow, and the consequent direction of particle movement 4;
  • Figure 2 illustrates a test planar interdigitated electrode pair comprising digits arranged at various angles to the direction of laminar flow
  • Figure 3 is an image of the electrode pair of Figure 2 having a liquid flow o particles over the surface without an applied electric field. The flow is from right to left at a slight downwards angle;
  • Figure 4 is an image of the electrode pair of Figure 2 having a l iquid flow of particles over the surface with an applied electric field. The flow is from right to left at a slight downwards angle. The vortices distort the (low and panicles accumulate at the downstream edge of each digit:
  • Figure 5 is a magnified trail of a single particle over the electrode pair of Figure 2 as compared to the direction of laminar flow. The data coincides with movement of the particle over the electrode digits which are at angles of 20° and 25° to the direction of laminar flow. The overall diversion from the direction of How is 1 1 .2°;
  • Figure 6 is a schematic of one embodiment of apparatus of the present invention.
  • a computer controlled three-channel syringe pump supplies l iquid to the flow chamber at a single inlet and removes l iquid from the flow chamber at two outlets.
  • a signal generator supplies the electrode arrangement with an alternating potential, and a microscope camera captures images for processing;
  • Figure 7 is a plot of light intensity at both outlets of the apparatus of Figure 6, and the ratio of light intensity at the outlets at a laminar How rate of 8.2 ⁇ /min.
  • the fluorescence is higher at one outlet with the ratio between outlets stabilising at an average of 2.75;
  • Figure 8 is a plot of light intensity at outlet 1 and outlet 2 of the apparatus of Figure 6, and the ratio of light intensity at the outlets at a laminar flow rate of 1 1 ⁇ /min, with the light intensity adjusted at the start of the experiment.
  • the fluorescence is higher at outlet 1 than outlet 2.
  • the ratio increases as the How pattern is established, and stabilises at an average of 2.2;
  • Figure 9 is a schematic of apparatus to investigate movement and concentration of particles in a flow chamber.
  • a computer controlled three-channel syringe pump supplies liquid to die How chamber al two inlets and removes liquid from the flow chamber at one outlet.
  • a signal generator supplies the electrode arrangement with an alternating potential, and a microscope camera captures images for processing;
  • Figure 10 a) and b) are images of liquid comprising fluorescent latex beads flowing through the flow chamber of the apparatus of Figure 9. The beads are the light area in the centre of the images, flanged by buffer on both sides.
  • Figure 10 a) is the liquid flow without applied electric field.
  • Figure 10 b) is the l iquid How with applied electric field;
  • Figure 1 1 a) and b) are graphs of fluorescence in the flow chamber of the apparatus of Figure 9 across the width of the flow chamber measured within a distance of 0 to 3 mm of the inlet ( Figure 1 1 a) and a distance within 8.5 to 1 1 .5 mm of the inlet, in the presence of fluorescent latex beads, and both with and without an applied electric field;
  • Figure 12 is a graph of the outlet concentration ratio for a 1 ⁇ 2 virtual split against flow cell depth with an electrode digit width of 200 ⁇ , al various flow rates;
  • Figure 13 is a graph of the outlet concentration ratio for a 1 ⁇ 2 virtual split against electrode digit width with a flow cell depth of 175 ⁇ , at various flow rates;
  • Figure 14 is a graph of the outlet concentration ratio for a 1 ⁇ 2 virtual split against electrode digit angle to the direction of the laminar (low with a flow cell depth of 1 75 ⁇ , and an electrode digit width of 400 ⁇ , at various flow rates;
  • Figure 15 is a graph of the outlet concentration ratio for a 1 ⁇ 2 virtual split against electrode digit gap with a flow cell depth of 175 ⁇ , and an electrode digit width of 400 ⁇ , at various flow rates;
  • Figure 16 represents the division of an inierdigitated electrode pair into cells for modelling purposes.
  • Figure 17 is a model for a 5 x 21 cell electrode digit system with redistribution factors of 1/3 and 2/3.
  • a first prototype apparatus was built and showed promising results. Digits of a planar inierdigitated electrode pair were angled approximately 1 ° lo the direction of flow containing 100 nm fluorescent latex beads. The experiment was recorded without and with an electric field appl ied to the electrodes. With the field applied the particles arranged into clearly visible bands of curved trajectory, il lustrating movement of particles out of the direction of the laminar How in the presence of induced electro- osmotic vortices in the liquid.
  • an electrode structure 5 was designed that allowed the testing of multiple angles at the same lime.
  • the electrode arrangement consisted of inlerdigitated electrodes (dark areas 6) radiating from a central point with an angle of 5° between neighbouring digits and a constant inter-digit gap (l ight areas 7) of 100 um.
  • visual inspection showed vortices to distort the flow and particles to clump and travel along the downstream edge of the digits, at an angle to the main liquid flow.
  • apparatus comprised a flow chamber having one inlet 1 0 and two outlets 1 1 , a planar inlerdigitated electrode pair at the base of the flow chamber, and a computer controlled three-channel pump system 12. Effects such as surface tension at the outlet of the flow chamber can have a significant effect on the flow ratio between outlets, leading to wildl y fluctuating ratios.
  • the three channel pump system provides a reproducible split of the l iquid at the outlets of the flow chamber, thus overcoming the problem of fluctuating How ratios.
  • the computer- controlled three-channel pump system was designed to pump liquid into the inlet of the flow chamber 1 3 while at the same time removing liquid at controlled flow rates from the outlets.
  • the set-up also comprises a signal generator 14 suppl ying the electrode arrangement 15 with an alternating potential, a microscope camera 1 6 to capture images of the electrode surface, and a computer 1 7 to control the whole system.
  • electrode structures were designed with various angles, digit widths and inter-electrode digit gaps, covering angles between 8°, 1 2°, 16°, 20° and 24°, digit widths of 100 ⁇ , 200 ⁇ , 400 ⁇ , 600 ⁇ and inter-electrode digit gaps of 50 ⁇ , ⁇ ⁇ ⁇ and 200 ⁇ . Selected devices were fabricated and tested to identify optimum conditions for concentration. Devices were tested with different How rates and flow chamber width.
  • fluorescence intensity in the two outlet streams Since the fluorescence of the stream is proportional to the concentration of particles within the stream, the ratio between the light intensity in the streams is proportional to the ratio of particle concentration.
  • the flow chamber has a volume of approximately 80 pL. Considering the range of flow rates analysed a volume of 144 pL per flow rate was chosen to be pumped through the chamber from the syringe pump system. The system was tested without appl ied field at the highest flow rate to make sure the flo chamber full y filled with particle suspension, and to measure intensity levels at the outlets. For each successive flow rate, 144 pL of liquid medium was pumped through the chamber with the applied field. The (low rale was decreased to the next How rale once a volume of 144 ⁇ had passed. To aid in comparison of the data, images were not captured at fixed time points, but instead at fixed volume points. In most experiments, images were captured every 1 pL.
  • the flow chamber does not separate the Hows at the outlet, but has two inlets 21 and only one outlet 22.
  • One of the inlet channels was split within the (low chamber to provide two further channels, allowing a channel containing beads to be pumped into the centre of the flow chamber, where it was sandwiched between two channels of buffer without beads. Comparing images with and without electric field allowed the trajectory of the beads to be traced precisely within the flow chamber.
  • the (low chamber comprises at its base a planar interdigilated electrode.
  • a microscope 1 6 with video system was setup to monitor the whole width of the flow chamber 1 3 and images were taken along the length of the flow chamber lo monitor how the distribution of beads changed along the flow chamber.
  • Electrodes with 400 um wide digit tracks, 100 urn gaps, 50 mm length and various electrode angles were tested to identify optimum conditions for separation.
  • Devices were tested with different flow rates and flow chamber width, images were anal ysed in two ways. Firstly, the distribution of particles against the width of the flow chamber was measured at di ferent points along the length of the (low chamber. Secondly, the boundary between buffer containing beads and buffer without beads was monitored close to the inlet, since it showed the movement of the vortex front.
  • the images show the stream of beads (light area in the centre of the image, 23) in the (low chamber, (Tanged by streams of clear buffer (dark area on both sides of the image, 24).
  • the sides of the (low chamber show as faint lines running close to the edge of the images.
  • Figure 10a shows the stream without a field, and Figure 10b with the field switched on. The How spreads in both directions with the field on, however the spread is not symmetrical, with more beads being pushed to the left of the image
  • the flow chamber design used two inlets and one outlet, allowing the flow of beads to be "sandwiched" between two How streams of buffer. This allows belter tracking of the particles, but also allows particles to Hood the whole width of the cell by disabl ing the flow of buffer. Since the flow regime inside the flow chamber is strictly laminar, 'virtual outlets' at different flow ratios could be extracted from the images.
  • the optical part of the system was designed to work without the use of a microscope, with the introduction of a video camera modified to view fluorescence. A 490 nm blue power LED was used to excite the fluorescent beads, whilst using a colour camera capable of separating the signal into red, green, and blue channels.
  • the concentration ratio achieved between each 'virtual outlet' was calculated as the ratio of fluorescence at the two outlets a ter the electric field was applied / the ratio of fluorescence at the two outlets before the electric field was applied. This approach was chosen since the ratio between outlets without an electric field was often more or less than 1 , and thus some compensation for this effect was required. This effect is believed to be caused by factors such as uneven excitation illumination, defects on the electrodes, or beads stuck to the surface of the (low chamber.
  • the distance of the gap between digits influences the strength of the electric field across the gap, and thereby the magnitude of the vortices at a given voltage.
  • the system performed best with a 100 ⁇ gap.
  • the device performed consistently well at flow rates of 4.1 or 6.2 ul/min. Broader flow chambers should sustain higher flow rates.
  • the examples show that redistribution of particles within the flow chamber does not happen continuously, but only at transitions over an electrode digit edge, when a vortex at the trailing edge of the electrode pushes the particle in the desired direction for concentration, and a vortex at the leading edge of each electrode digit pushes panicles away from the desired direction, in fact pushing particles off course.
  • the laminar flow distorts the vortices at the edges, however the particles exhibit a wave- shaped trajectory in the desired direction for concentration as the vortex at the trail ing edge is prominent.
  • the phenomenon providing movement of particles is therefore not continuous but can be broken down into cells containing a single redistribution step comprising one transition in the direction of the (low and one perpendicular to the (low.
  • Each cell passes on a proportion of the particle concentration to neighbouring cells, based on a redistribution factor at both the leading edge and at the trailing edge of an electrode digit.
  • a redistribution factor is a numerical indication for the proportion of particle concentration that is directed towards neighbouring cel ls.
  • the redistribution factor at the trail ing edge will be higher (e.g. 2/3 ) than that for the leading edge (e.g. 1 /3), since the vortex at the trailing edge is more prominent.
  • the cells at the edges of the flow chamber can only pass in one direction since there is only a single neighbouring cell . In this case a proportion of the particle concentration remains in the cell at the edge of the flow chamber. This results in particles slowly shi fting towards one edge of the flow chamber.
  • This model explains the build up of particles along one edge but it also explains why the system reaches equilibrium.
  • Model and experimental results show a good match, based on redistribution factors of 1 /3 and 2/3 , even though the experimental results show less l inear growth at the high concentration side of the flow chamber and less depletion at the low concentration side.
  • the maximum concentration ratio that can be achieved depends on the redistribution factors between the cells, however further modelling has confirmed that it also depends on the number of cells along the width of the (low chamber. Increasing this number leads to a higher concentration ratio. Therefore the efficiency can be improved by making the (low chamber wider lo fit more electrode digits along the width. It also explains why shallower angles such as 15° work better since at shallower angles more cells can be accommodated across the width of the flow chamber. This also matches experimental data where the 200 urn wide electrodes provide better results than wider electrodes.
  • the model also predicts that the band containing the highest concentration should be about the width of one cell, In our system with optimum choice of parameters this would equate to about 1 /22 of the How chamber width. This is confirmed by revisiting the ' virtual outlet' distribution model, where the concentration starts to plateau at approximately a 1/20 How split ratio, with a theoretical 7-fold improvement in concentration.
  • the minimum requirement for driving a particle out of laminar liquid flow is a pair of parallel electrodes eparated by a gap of a predetermined distance, wherein the electrodes align at an angle to the direction of laminar liquid flow.
  • the effect is however more pronounced, and more effective, when multiple pairs of electrodes parallel with respect to each other are provided.
  • the multiple pair of electrodes may conveniently be provided by an interdigitated electrode pair, wherein the digits of the interdigitated electrode pair correspond to the multiple pairs of electrodes.

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Abstract

La présente invention se rapporte à la concentration de particules dans un écoulement de liquide par le déclenchement de tourbillons électro-osmotiques dans l'écoulement de liquide, et en particulier à un appareil comprenant une paire d'électrodes planes interdigitées, lesdites électrodes étant alignées selon un angle dans la direction d'écoulement de liquide laminaire et étant entraînées par un potentiel alternatif ; ce qui permet à ladite paire d'électrodes interdigitées de déclencher des tourbillons électro-osmotiques pour modifier la direction de particules dans l'écoulement de liquide, et ce qui permet la concentration des particules dans l'écoulement de liquide.
PCT/GB2010/001751 2009-09-22 2010-09-20 Concentration de particules dans un écoulement de liquide WO2011036433A1 (fr)

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GBGB0916593.7A GB0916593D0 (en) 2009-09-22 2009-09-22 Particle concentration in a liquid flow
GB0916593.7 2009-09-22

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WO2015174834A1 (fr) 2014-05-12 2015-11-19 Hj Forever Patents B.V. Afficheur électro-osmotique
CN110366451A (zh) * 2017-04-23 2019-10-22 惠普发展公司有限责任合伙企业 颗粒分离
CN114007867A (zh) * 2019-06-25 2022-02-01 惠普发展公司，有限责任合伙企业 具有通道的模制结构

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015174834A1 (fr) 2014-05-12 2015-11-19 Hj Forever Patents B.V. Afficheur électro-osmotique
NL2012802B1 (en) * 2014-05-12 2016-02-24 Hj Forever Patents B V Electro-osmotic display.
CN110366451A (zh) * 2017-04-23 2019-10-22 惠普发展公司有限责任合伙企业 颗粒分离
US11325125B2 (en) 2017-04-23 2022-05-10 Hewlett-Packard Development Company, L.P. Particle separation
CN114007867A (zh) * 2019-06-25 2022-02-01 惠普发展公司，有限责任合伙企业 具有通道的模制结构
US11780227B2 (en) 2019-06-25 2023-10-10 Hewlett-Packard Development Company, L.P. Molded structures with channels
CN114007867B (zh) * 2019-06-25 2024-04-16 惠普发展公司，有限责任合伙企业 具有通道的模制结构
US12134274B2 (en) 2019-06-25 2024-11-05 Hewlett-Packard Development Company, L.P. Molded structures with channels

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GB2473750A (en) 2011-03-23
GB201015712D0 (en) 2010-10-27
GB0916593D0 (en) 2009-10-28

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