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    • 专利摘要:
    Abstract A macrosphere comprising a core and an outer skin, the core of the macrosphere having a diameter of between 30mm and 55mm and the outer skin of the macrosphere comprising epoxy reinforced with hollow glass microspheres of 20 microns diameter. A buoyancy material is also described comprising a combination of syntactic foam or gas-blown foam and a plurality of said macrosheres. A method of producing said macrospheres comprises placing a macrosphere core in a rotating drum and tumbling said core whilst epoxy resin and hollow glass microspheres are introduced into the drum to form a skin over the core. li IAIIhA ')A OalgAqAA I 2AA I I I
    公开号:AU2013200418A1
    申请号:U2013200418
    申请日:2013-01-25
    公开日:2013-11-14
    发明作者:Robert Kenneth Oram
    申请人:Balmoral Comtec Ltd；
    IPC主号:B29D22-04
    专利说明:
    AUSTRALIA Patents Act 1990 ORIGINAL COMPLETE SPECIFICATION STANDARD PATENT Invention title: Macrospheres The following statement is a full description of this invention, including the best method of performing it known to us: DUWM 24110280-v1 120324111 1 MACROSPHERES [0001] This invention relates to macrospheres and more particularly to buoyancy materials incorporating macrospheres and more particularly still to such materials for use in controlling the buoyancy of a body used to control the position or submerged weight of a flow line or riser used in the transport of hydrocarbons. [0002] In the production of hydrocarbons from offshore reservoirs, risers are established which extend between the seabed production facility and a surface based operation such as a drilling vessel, floating facility or fixed structure or FPSO or between two surface based vessels. The risers typically comprise of flexible pipe which carries fluids or umbilicals which carry power, fluids and/or control signals between the surface and subsea operations. [00031 In some cases it is necessary to control the configuration that the riser adopts as it extends up through the water. Typically buoyancy modules are connected to the riser at selected points in order to achieve a particular configuration of the riser. For flexible risers and umbilicals, typical configurations include Lazy Wave, Steep Wave, Pliant and W-Wave. These configurations are achieved by selectively controlling the positioning of the buoyancy modules along the riser such that the buoyancy elements provide lift to the riser and create the necessary riser wave configuration required to disconnect the seabed and surface vessel interfaces with the riser from the tension loads that would otherwise result from vessel and riser movements associated with active sea states. [0004] In some circumstances, rigid steel pipe is used as the riser, with the riser forming a continuous curve between the surface facility and the seabed. This configuration is called a 'catenary riser'. Here buoyancy is used to reduce the submerged weight of the riser thereby reducing the tension load on the riser termination at the surface facility. [0005] Finally, it is sometimes necessary to reduce the submerged weight of a section of seabed steel flowline in order to promote lateral buckling in a controlled manner as the flowline axially expands during the start of transportation of hot reservoir fluids. Buoyancy modules are positioned along selected lengths of flowline to create minimal submerged weight in these lengths and so facilitate lateral displacement at these selected locations.
    2 [0006] The buoyancy modules generally comprise an internal clamping system and syntactic foam buoyancy elements. The buoyancy elements may be supplied in two halves incorporating a moulded internal recess that is configured to transfer the forces from the buoyancy elements to a separate clamp within the internal cavity and subsequently to the flow line. Alternatively, clamping members may be attached to the inside surface of the buoyancy elements, such that the tensioning of the system holding the elements together also acts to create a clamping force for the module on the riser or flowline. [0007] By reducing the density of the syntactic foam used in fabricating the body of the buoyancy elements, the overall weight of the buoyancy modules can be reduced, thereby reducing the volume of foam and product size required to provide the same uplift, which in turn reduces the overall cost of production of the buoyancy modules. Reduction in product size for a given uplift may offer additional operational benefits such as reduced drag from ocean currents during operation or reduced dynamic loads from active sea states during launch of the buoyancy module. [0008] Syntactic foams typically comprise a combination of large macrospheres typically of around 40mm diameter core which are encapsulated in a matrix of pure syntactic (thermoset or thermoplastic resin filled with low density spheres). The scope for reducing the density of the pure syntactic is limited by the small number of glass microsphere grades of suitable pressure ratings for the particular service and therefore any desired reduction in the density of the macrosphere-containing syntactic foam must primarily come from reduction in density of the macrospheres. [0009] Macrospheres have a hydrostatic collapse resistance ('Burst Pressure') and by improving this resistance it is expected that a lower density of macrospheres can be used at a particular depth thereby providing a reduction in density of the macrosphere-containing foam and thereby a reduction in overall weight of the modules with the associated cost saving this produces. [0010] Macrospheres of a core diameter up to a maximum of 12mm which have an outer epoxy skin which is reinforced with hollow glass microspheres have been produced in the past. The rate of increase of the Burst Pressure as the density increases of these macrospheres was however low, due to the irregularity in shape of the expanded polystyrene (EPS) core used for production of 3 macrospheres of this diameter and the production difficulties of microsphere based macrospheres of this diameter. For larger macrospheres with a core diameter of 30mm or above, where uniform spherical EPS cores are available, production of macrospheres based on hollow glass microspheres having a diameter of typically around 30 microns has previously only resulted in macrospheres with a relatively low pressure gradient rating signifying a low rate of increase of Burst Pressure with an increase in density. [0011] The reason for this low pressure rating is that the hollow glass microspheres in the surface of the macrospheres previously manufactured were increasingly ground down by impact and abrasion between macrospheres as the macrosphere density increases. In other words, the macrosphere skin progressively became epoxy reinforced with broken glass rather than epoxy reinforced with hollow glass microspheres. [0012] Therefore it is an aim of the present invention to improve the hydrostatic collapse resistance of macrospheres of any given density. [00131 According to one aspect of the present invention there is provided a macrosphere comprising a core and an outer skin, the core of the macrosphere having a diameter of between 30mm and 55mm and wherein the outer skin of the macrosphere comprises epoxy reinforced with hollow glass microspheres of 20 microns diameter. [0014] Preferably the core of the macrosphere has a diameter of at least 35mm. [0015] More preferably the core of the macrosphere has a diameter of between 40mm and 50mm. [0016] Advantageously the microspheres have a 50% by diameter of below 20 microns. [0017] More preferably the microspheres have a 50% by diameter of between 14 and 18 microns. [0018] Preferably the reinforcing is provided by one or more layers comprising microspheres.
    4 [0019] Preferably also the reinforcing layer comprises an epoxy resin. [0020] Preferably the thickness of a layer of microsphere-containing composite laid down per coating stage in a multi-layering process for the macrosphere is a minimum of 25 microns. [0021] Preferably the layer has a thickness of between 33-38 microns. [0022] Preferably the core of the macrosphere comprises a low density foam. [00231 Advantageously the core comprises expanded polystyrene (EPS). [0024] According to a further aspect of the present invention there is provided a buoyancy material comprising a combination of syntactic foam or gas blown foam and a plurality of macrospheres according to the first aspect of the present invention. [0025] Preferably the syntactic foam comprises an epoxy syntactic foam. [0026] Preferably the gas-blown-foam comprises polyurethane or polyisocyanurate foam. [0027] According to a still further aspect of the present invention there is provided a buoyancy module comprising a buoyancy material according to the second aspect of the present invention. [0028] According to a fourth aspect of the present invention there is provided a method of producing a macrosphere according to the first aspect of the invention comprising placing a macrosphere core in a rotating drum and tumbling said core whilst epoxy resin and hollow glass microspheres are introduced into the drum to form a skin over the core. [0029] Advantageously the core is tumbled whilst epoxy resin and glass fibres are introduced to create a macrosphere coated with fibre-reinforced epoxy prior to introducing the epoxy resin and hollow glass microspheres into the drum.
    5 [00301 The earlier provision of a glass fibre reinforced epoxy coating on the core improves the efficacy of the subsequent coating processes using hollow glass microspheres. [00311 Preferably the production method further comprises forming the skin on the macrosphere via a multi-layering process. [0032] Preferably the layers of the skin comprising epoxy resin and hollow glass microspheres may be build up on the core until the macrosphere density reaches approx. 300kg/m 3 . [00331 Advantageously further layers may be built up on the macrosphere, said further layers having a different composition to the layers of epoxy and hollow glass microspheres. [0034] Preferably the method further comprises the step of introducing glass reinforced epoxy or carbon fibre reinforced epoxy into the drum to form said further layers on the macrosphere. [0035] An embodiment of the present invention will now be described with reference to the accompanying drawings in which: [0036] Figure 1 is a graph showing the burst pressure verses density of a macrosphere according to one embodiment of the present invention which uses microspheres of 50% by diameter of 16 microns against a macrosphere reinforced with glass microspheres of 50% by diameter of 30 microns; [0037] Figure 2 is a graph showing the burst pressure verses density of a macrosphere according to an embodiment of the present invention which uses macrospheres reinforced with glass microspheres of 50% by diameter of 16 microns and macrospheres with a core diameter of 40mm reinforced with carbon fibre; [0038] Figure 3 is a graph showing the diameter verses density of a macrosphere according to one aspect of the present invention which uses microspheres of 50% by diameter of 16 microns against a carbon fibre-reinforced macrosphere and a glass-fibre reinforced epoxy macrosphere, and 6 [00391 Figure 4 is a graph showing the diameter verses density of a macrosphere according to one embodiment of the present invention which uses microspheres of 50% by diameter of 16 microns against a macrosphere reinforced with glass microspheres of 50% by diameter of 30 microns. [0040] As indicated above, in the past for larger macrospheres with a core diameter of 30mm or above, production of these macrospheres based on hollow glass microspheres has previously only resulted in macrospheres with a relatively low pressure gradient rating due to the continual grinding down of the microspheres in the outer layers of the macrospheres. [0041] A macrosphere according to one embodiment of the present invention comprises a core of pre-formed, spherical low density foam having a density of around 6-50 kg/m 3 and in the preferred embodiment has an expanded polystyrene (EPS) core. The pre-moulded EPS core provides an accurately spherical surface onto which a reinforced composite can be layered during a multi-layering macrosphere manufacturing process. EPS is selected because of its ability to be accurately moulded into a uniform sphere, its low cost and its high compressive strength/rigidity even at low densities. [0042] The macrosphere has an EPS core diameter of between 30mm to 55mm and has an outer skin of epoxy resin which in part is reinforced with hollow glass microspheres in place of the standard fibre reinforcement provided on conventional macrospheres. The microspheres have a 50% by diameter of 520 microns and in the examples given below the microspheres have a 50% by diameter of 16 microns. [00431 To produce the outer skin, layers of glass-fibre reinforced epoxy is laid down on the core of the macrosphere. This is done by tumbling the EPS cores in a rotating drum or rotating bed with a quantity of epoxy resin and milled glass-fibre. Preferably about 4-6 of such layers are built up on the EPS cores. This serves to seal the EPS surface of the core and also to provide some weight to the otherwise very light EPS spheres. This also gives the macrosphere a smooth, even surface for the subsequent build up of layers of microsphere-reinforced epoxy. [0044] Subsequent layers of microsphere-reinforced epoxy of at least 25 microns and preferably between 33-38 microns are then built up on the macrosphere by tumbling the glass-reinforced epoxy coated EPS cores in the 7 rotating drum with a quantity of epoxy resin and glass microspheres until the density of the macrospheres reach approx. 300kg/m 3 . Further layers may at this time be built up by reverting to more conventional and therefore generally more cost effective reinforcements such as carbon fibre reinforced epoxy or glass reinforced epoxy and still retain the superiority achieved up to that point as will be demonstrated further below. [0045] For example the thickness of individual coats of resin and microspheres on a 40mm EPS macrosphere cores may be around 35microns using microspheres with 50% by diameter 16 microns. This small diameter relative to the thickness of the composite layer allows the individual microspheres to be afforded far greater protection against attrition damage than is possible with 'standard' glass microsphere grades of much greater diameter. [0046] Using the process as described above over 100,000 macrospheres according to the present invention can be produced in a single batch in 24-36 hours. [0047] By reinforcing the outer skin of the macrospheres with hollow glass microspheres, the macrosphere is provided with a significantly lower density skin than previously available, which means that the thickness of the skin can be increased beyond that of a comparable fibre-reinforced macrosphere without increasing the overall density of the macrosphere. By way of example with a macrosphere of nominal 40mm EPS core diameter and an epoxy skin reinforced with microspheres of 16 microns, the density of the microsphere-reinforced skin will be approximately 1.0 - 1.1g/ml, compared to 1.35 - 1.45g/ml for a carbon fibre-reinforced skin and 1.9 - 2.1g/ml for a glass fibre-reinforced skin. [0048] Figure 1 is a graph which charts the performance of macrospheres produced with 2 different grades of hollow glass microspheres each having a density of 0.6g/ml. The upper plot line represents a macrosphere in which the outer skin is reinforced with microspheres of 50% by diameter of nominal 16 microns according to one embodiment of the present invention and the lower plot line represents a macrosphere in which the outer skin is reinforced with microspheres of 50% by diameter of nominal 30 microns. [0049] The macrosphere reinforced with microspheres of only 50% by diameter of 16 microns shows significantly superior performance as measured by 8 the Burst Pressure to the macrosphere reinforced with much larger microspheres, in this case a 50% by diameter of 30 microns, despite both microspheres having the same density. [0050] As can be seen on the graph, the performance of a macrosphere incorporating a skin reinforced with the larger microspheres as measured by rate of burst pressure improvement with pressure is falling as the density increases. In other words, the gradient of the improvement in burst pressure rating is low. However the performance of the macrosphere reinforced with the smaller microspheres again measured by rate of burst pressure improvement with pressure is increasing with density and therefore the gradient of the improvement in burst pressure is substantially higher than for the macrosphere reinforced with larger microspheres. [0051] This is attributed to the larger microspheres suffering greater attrition damage at all stages and also progressively increasing attrition damage at higher densities. This greater attrition damage in the larger microspheres leads to proportionately higher reinforcement of the macrosphere composite skin with the much denser broken glass from the destroyed microspheres rather than intact microspheres. The resultant composite skin is significantly denser and therefore thinner for a given macrosphere density. The thinner skin for a given density results in a reduced gradient of increase in macrosphere Burst Pressure over density as shown in Figure 1. [0052] Such low density, thicker walled macrospheres of the present invention also out-perform macrospheres produced with a conventional fibre reinforcement including carbon fibre which previously has been recognised as producing the highest performing macrospheres. Carbon fibre is traditionally used to manufacture macrospheres of high hydrostatic burst pressure and thereby syntactic foams of low density. [00531 Figure 2 is a graph illustrating the curve for burst pressure versus density for a macrosphere according to the present invention with a reinforced skin of microspheres of 16 microns by diameter (the upper plot line) plotted against the typical burst pressure vs density line for carbon fibre-reinforced macrospheres (the lower plot line) which clearly illustrates this improvement in performance such that the density of a macrosphere according to this example of the present invention with a burst pressure of 3500 psi is around 290 kg/m 3 9 whereas for a carbon fibre reinforced macrosphere with a 40 mm core diameter, the density required to reach the same burst pressure is 320 kg/m 3 . [0054] Furthermore, as noted above, even where the production process is modified once the density of the macrosphere reaches approx. 300kg/m 3 such that subsequent layers are provided from more conventional and therefore generally more cost effective reinforcements such as carbon fibre, the significant performance improvement achieved by incorporating the microspheres of . 20 microns as described above in the earlier reinforcement layers is retained as the density of the macrospheres increases. Therefore a macrosphere according to the present invention with additional layers of conventional reinforcement continues to out-perform a macrosphere of similar density by the same amount as was achieved by incorporating the smaller diameter glass microspheres into the initial coating layers. [0055] As shown in Figure 2, the burst pressure of the macrospheres according to examples of the present invention is higher than that of a similar density macrosphere with a conventional fibre-reinforced skin. This allows for a significantly lower density of macrosphere to be used for any given service depth and hydrostatic pressure, by maintaining the essential minimum burst pressure associated with lifetime service. The use of macrospheres of lower density in turn provides the significant advantages of reduction in overall weight and product cost, without loss of performance as already described. [0056] Figure 3 is a graph showing Diameter vs. Density for a macrosphere according to the present invention with the outer skin reinforced with microspheres of 50% by diameter of nominal 16 microns (the upper plot line), a macrosphere with an outer skin of carbon fibre reinforced epoxy (CFRE) (the middle plot line) and a rotationally moulded macrosphere with an outer skin of glass reinforced epoxy (GRE) (the lower plot line) which shows the improvements in diameter and thereby skin thickness of a macrosphere achieved by the present invention. [0057] Figure 4 is a graph showing the same information as Figure 3 for the 2 macrospheres of Figure 1 in which the upper line represents the plot line of the macrosphere according to the present invention showing a consistently thicker skin than a macrosphere of the same density but as earlier described.
    10 [0058] The collapse pressure of a macrosphere is proportional to the square of the skin thickness and also to the modulus of elasticity of the composition of the skin and therefore the pressure rating of a macrosphere having a thicker outer skin (reflected in increased outside diameter for a fixed EPS core size) is greatly superior to one having a thinner outer skin of the same composition but having the same macrosphere overall density. [0059] By incorporating the macrospheres as described above into a buoyancy material comprising syntactic foam or non-syntactic (gas-blown) foam, the operator is able to reduce the density of the composite (macrosphere containing) syntactic foam material from which buoyancy modules are formed and by reducing the density of the syntactic foam used in forming the body of the buoyancy modules, the overall weight of the modules can be reduced, thereby reducing the volume of foam required to provide the same lift which in turn reduces the overall cost of the buoyancy modules produced. [0060] Furthermore, by improving the hydrostatic collapse resistance of the macrospheres across the entire range of macrosphere densities, a lower density of macrospheres can be used in the buoyancy material at any particular depth. With the standard fibre reinforcements such as Carbon and Glass, the density of macrosphere required to tolerate the most extreme depths of beyond 3000 metres becomes so high that the density advantage of the macrosphere-containing foam relative to the unfilled (macrosphere-free) syntactic foam is significantly reduced. The major improvement in burst performance (hydrostatic pressure resistance) of the hollow glass microsphere-containing macrosphere of the present invention allows the use of relatively low density macrospheres even at the most extreme depths, which further increases the range of operation of the lower cost composite foam buoyancy modules. Macrospheres according to the present invention having a pressure rating suitable for service at 15000ft can be produced which is a significant improvement of standard macrospheres. [0061] By providing a macrosphere with an EPS core diameter of between 30mm and 55mm and providing an outer skin on the macrosphere of a thermosetting plastic such as epoxy reinforced with hollow glass microspheres as described above, an improvement in the hydrostatic collapse resistance of the macrospheres has been observed as is clear from a comparison of Figures 1 and 2.
    11 [0062] Whilst a macrosphere of this increased size having such a hollow glass microsphere reinforced outer skin will still undergo some attrition damage as described above in relation to smaller macrospheres, by limiting the size of the hollow glass microspheres to 20 microns in a composite layer of minimum 25 microns and typically 35 microns thickness, this attrition damage is reduced, as a smaller percentage of the microspheres are directly exposed to attrition and therefore survive for maximum performance of the material. Therefore large scale production of macrosphere using EPS macrosphere cores of between 30mm to 55mm and microspheres of 520 microns will have a greatly superior performance than those produced with a similar density but a larger diameter microsphere [00631 It is envisaged that the macrospheres according to the first aspect of the invention will be incorporated into buoyancy materials comprising syntactic and non-syntactic foams from which components such as buoyancy elements for use in the control of the buoyancy or submerged weight of subsea risers and flowlines, particularly for use in the transportation of hydrocarbons can be formed.
    权利要求:
    Claims (25)
    [1] 1. A macrosphere comprising a core and an outer skin, the core of the macrosphere having a diameter of between 30mm and 55mm and wherein the outer skin of the macrosphere comprises epoxy reinforced with hollow glass microspheres of 20 microns diameter.
    [2] 2. A macrosphere according to claim 1, wherein the core of the macrosphere has a diameter of at least 35mm.
    [3] 3. A macrosphere according to claim 2, wherein the core of the macrosphere has a diameter of between 40mm and 50mm.
    [4] 4. A macrosphere according to any of the preceding claims, wherein the microspheres have a 50% by diameter of below 20 microns.
    [5] 5. A macrosphere according to claim 4, wherein the microspheres have a 50% by diameter of between 14 and 18 microns.
    [6] 6. A macrosphere according to any of the preceding claims wherein the outer skin is provided a plurality of layers comprising microspheres.
    [7] 7. A macrosphere according to claim 6 wherein the reinforcing layers comprises an epoxy resin.
    [8] 8. A macrosphere according to claim 6 wherein the thickness of a layer of microsphere-containing composite laid down per coating stage in a multi layering process for the macrosphere is a minimum of 25 microns.
    [9] 9. A macrosphere according to claim 8, wherein the layer has a thickness of between 33-38 microns.
    [10] 10. A macrosphere according to any of claims 1-9, wherein the core of the macrosphere comprises a low density foam.
    [11] 11. A macrosphere according to claim 10, wherein the core comprises expanded polystyrene (EPS). 13
    [12] 12. A macrosphere substantially as hereinbefore described.
    [13] 13. A buoyancy material comprising a combination of syntactic foam or gas blown foam and a plurality of macrospheres according to any of claims 1 12.
    [14] 14. A buoyancy material according to claim 13, wherein the syntactic foam comprises an epoxy syntactic foam.
    [15] 15. A buoyancy material according to claim 13, wherein the gas-blown-foam comprises polyurethane or polyisocyanurate foam.
    [16] 16. A buoyancy material substantially as hereinbefore described.
    [17] 17. A buoyancy module comprising a buoyancy material according to any of claims 13-16.
    [18] 18. A buoyancy module substantially as hereinbefore described.
    [19] 19. A method of producing a macrosphere according to any of claims 1-12 comprising placing a macrosphere core in a rotating drum and tumbling said core whilst epoxy resin and hollow glass microspheres are introduced into the drum to form a skin over the core.
    [20] 20. A method of producing a macrosphere according to claim 19, wherein the core is tumbled whilst epoxy resin and glass fibres are introduced to create a macrosphere coated with fibre-reinforced epoxy prior to introducing the epoxy resin and hollow glass microspheres into the drum.
    [21] 21. A method of producing a macrosphere according to claim 19 or 20 comprising forming the skin on the macrosphere via a multi-layering process.
    [22] 22. A method of producing a macrosphere according to claim 21 in which layers of the skin comprising epoxy resin and hollow glass microspheres are build up on the core until the macrosphere density reaches approx. 300kg/m 3 . 14
    [23] 23. A method of producing a macrosphere according to claim 22, wherein further layers are built up on the macrosphere, said further layers having a different composition to the layers of epoxy and hollow glass microspheres.
    [24] 24. A method of producing a macrosphere according to claim 23, comprising the step of introducing glass reinforced epoxy or carbon fibre reinforced epoxy into the drum to form said further layers on the macrosphere.
    [25] 25. A method of producing a macrosphere substantially as hereinbefore described.
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    同族专利:
    公开号 | 公开日
    AU2013200418B2|2013-12-12|
    GB201207356D0|2012-06-13|
    BR102013004705A2|2015-07-14|
    GB2499683A|2013-08-28|
    BR102013004705B1|2020-09-01|
    GB2499683B|2014-03-12|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CN103665768A|2013-11-26|2014-03-26|上海复合材料科技有限公司|Method for preparing high-strength solid buoyancy material|
    CN105980143A|2014-02-13|2016-09-28|3M创新有限公司|Flexible microsphere articles having high temperature stability|US4021589A|1976-04-28|1977-05-03|Emerson & Cuming, Inc.|Buoyancy materials|
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    US7867613B2|2005-02-04|2011-01-11|Oxane Materials, Inc.|Composition and method for making a proppant|AU2017322100A1|2016-09-05|2019-04-04|Matrix Composites & Engineering Ltd|Lightweight concrete|
    CN107573482A|2017-10-18|2018-01-12|青岛海洋新材料科技有限公司|A kind of polyurethane buoyant material and preparation method thereof|
    CN110655777A|2019-10-16|2020-01-07|郭建中|Polyurethane-nano Al2O3Composite coated hollow glass microsphere|
    法律状态:
    2014-04-10| FGA| Letters patent sealed or granted (standard patent)|
    优先权:
    申请号 | 申请日 | 专利标题
    GB1207356.5||2012-04-27||
    GB1207356.5A|GB2499683B|2012-04-27|2012-04-27|Macrospheres|
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