CN101506113B - Bushing for production of glass continuous filament and manufacture method thereof, equipment for producing glass continuous filament and process for production of the filament using the equipment - Google Patents
Bushing for production of glass continuous filament and manufacture method thereof, equipment for producing glass continuous filament and process for production of the filament using the equipment Download PDFInfo
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- CN101506113B CN101506113B CN2007800313023A CN200780031302A CN101506113B CN 101506113 B CN101506113 B CN 101506113B CN 2007800313023 A CN2007800313023 A CN 2007800313023A CN 200780031302 A CN200780031302 A CN 200780031302A CN 101506113 B CN101506113 B CN 101506113B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/08—Bushings, e.g. construction, bushing reinforcement means; Spinnerettes; Nozzles; Nozzle plates
- C03B37/095—Use of materials therefor
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Abstract
To provide a bushing of strong structure which is reduced in the quantity of substance evaporated from the bushing and enables the formation of high-precision glass filaments. A bushing (1) for producing glass continuous filaments (F) by making molten glass (G) flow out through nozzles (6) of a bushing plate (4), wherein a coating film (7) made of a material selected from the group consisting of ceramics, glass-ceramics and glass covers the outside surface of the bushing plate (4) except the outer peripheral surfaces of the nozzles (6) and the end face; a process for the production of glass continuous filaments by producing glass filaments for composite materials with the bushing (1) while watching the outside surface of the bushing plate (4) and the state of spinning; and a process for the production of the bushing (1) which comprises the bushing body formation step of assembling a bushing body (2), the coating step of forming a coating on at least the outside surface of the bushing plate (4) of the bushing body (2), and the baking step of heating the coating to convert it into a dense-structure film.
Description
Technical field
The bushing that the present invention relates to when forming continuous glass fibre, to use and the method for manufacture of this bushing, be the continuous glass fibre manufacturing installation of main component parts and the method for manufacture that has adopted the continuous glass fibre of this device, particularly relate to the improvement of continuous glass fibre manufacturing with the outer surface properties of bushing with this bushing.
Background technology
Generally speaking; Spun glass roughly can be divided into short glass fiber and continuous glass fibre clearly; For to above-mentioned among both reliably the continuous glass fibre except short glass fiber form or during spinning, can use to be referred to as the stable on heating band of having of " bushing " and to be shaped with the container of nozzle.This bushing uses in order to be configured as melten glass fibrous; Wherein, In the bottom of bushing surrounding wall portion fixedly bushing plate (bushing plate) to form bushing main body (container body); And be that melten glass is supplied with the space, and set up to make at the bottom surface side of bushing plate and supplied with the many nozzles that the spatial melten glass flows out from melten glass with the inside of this bushing main body.Then; Through flowing out melten glass continuously and form many glass strands (continuous glass fibre) respectively from these many nozzles; When after the coating agent of surface-coated collecting agent (boundling drug) of this glass strand etc., through making the fibre product that forms by continuous glass fibre with winding machine coiling single thread.
In order to make various high-quality continuous glass fibres continuously and sleekly through above-mentioned operation, the bushing that need be complementary with the desired performance of the continuous glass fibre of wanting to make, shape or size etc.Therefore, during till today, many inventions have been made to bushing and the nozzle that sets on it.For example, disclose in patent documentation 1, the patent documentation 2 a kind of be used to make have aspect ratio and use injector head in the spinning of the continuous glass fibre of the deformed sections shape more than 2 or more than 4.In addition, if the bushing plate remains under the condition of high temperature for a long time, softening and deterioration can take place then, the sagging distortion of weight because of deadweight or melten glass still, discloses a kind of supporting device that is used to prevent this distortion in the patent documentation 3.And disclosing a kind of outside surface at nozzle in the patent documentation 4, to implement cyclic concavo-convex and make the stable invention of heat dispersion.In addition, disclose a kind of groove through forming the degree of depth 0.5～50 μ m at nozzle outer surface or concavo-convex in patent documentation 5, the patent documentation 6, thereby prevented because of the cut-out of oozing out caused continuous glass fibre of melten glass to nozzle outer surface.In addition, disclose a kind ofly in order to prevent the volatilization of precious metal in the patent documentation 7, and bushing is used in the spun glass manufacturing of at least 1 layer composition formation that changes the proportion of composing of pottery and precious metal at the Tou Banchu of bushing gradually.
Patent documentation 1: TOHKEMY 2000-335932 communique
Patent documentation 2: TOHKEMY 2000-344541 communique
Patent documentation 3: japanese kokai publication hei 02-097433 communique
Patent documentation 4: japanese kokai publication hei 02-153837 communique
Patent documentation 5: japanese kokai publication hei 04-083730 communique
Patent documentation 6: japanese kokai publication hei 04-083731 communique
Patent documentation 7: japanese kokai publication hei 06-298543 communique
But, only enumerate above-mentioned invention and can't prove absolutely problem, but being continuous glass fibres, practical situation are widely used in the various uses.In recent years since; Along with than the Fibre diameter of high precision management continuous glass fibre more in the past; Under the situation that form in order to make continuous glass fibre be used as matrix material; Further require the intensity of this matrix material higher and can realize stable performance, in many purposes, need have than the continuous glass fibre of high-precision size in the past.Therefore, in order to make continuous glass fibre, carried out the research of the bushing that adapts with it more with such high precision size.Here; The problem that exists is a variety of causes that influences glass fiber diameter; But; The diameter of continuous glass fibre is not simple only to be decided by the dimensional precision in the aperture of nozzle opening portion, its also receive bushing high temperature under through the time distortion or the temperature when constituting evaporation and the extraction spun glass of material of bushing and the influence of various key elements such as speed or atmosphere.Therefore, need to investigate one by one very patiently to improve these key elements.The inventor in order to improve such variety of issue through discovering; As patent documentation 7, become high precision for Fibre diameter adjustment with continuous glass fibre; Be all the time to the improvement of the structure of nozzle, size etc. as a rule, and whether the countermeasure of thoroughly improving also exist other approach, promptly not as being based on the bushing board position outside the nozzle; Here, a kind of new technological thought is disclosed.
Summary of the invention
The objective of the invention is to; Provide a kind of evaporant that bushing under the high temperature is formed to reduce; And through forming bushing securely; Can pass through long-time be shaped with the condition of high temperature or spinning has the continuous glass fibre of high-precision Fibre diameter, thereby the matrix material that can make excellent quality is used continuous glass fibre.
Use bushing for addressing the above problem the continuous glass fibre manufacturing of initiating that the present invention relates to; It is that bushing is used in the continuous glass fibre shaping that is described below; Inside has melten glass and supplies with spatial bushing main body; Possess bushing surrounding wall portion and the bushing plate that is equipped on the bottom of this bushing surrounding wall portion; And set up to be useful at the bottom surface side of above-mentioned bushing plate and supply with the many nozzles that the spatial melten glass flows out to the shaping continuous glass fibre makes from above-mentioned melten glass; It is characterized in that, be formed with overlay film except the periphery of said nozzle and the outside surface of the above-mentioned bushing plate the end face, this overlay film has used any the above material in pottery, glass-ceramic and the glass material group.
According to such structure; Constitute the outside surface of continuous glass fibre manufacturing with the bushing plate of the bushing main body of bushing; Utilization comprises the structure spare of any one material in pottery, glass-ceramic (also being called sintered glass ceramics) or the glass; The method of the outward appearance through being coated with into the overlay film shape waits and applies, and on the contrary, the periphery and the end face of nozzle that is attached to the bottom surface side of bushing plate is not formed with such overlay film.
For the fact that has adopted such structure is described; The inventor has investigated from the evaporation of continuous glass fibre manufacturing with the drain board material of the outside surface of bushing; The result finds that it may not be the evaporation from nozzle, with evaporation from the bushing plate around it bigger relation is arranged on the contrary.In addition, nozzle self through so far many improvement methods and can obtain corresponding countermeasure, but position is not in addition obviously had countermeasure.So; The present invention is based on following aspect; Not to nozzle but, apply its surperficial privileged site, prevent from the Evaporation Phenomenon by the time under the hot environment of the bushing panel material of the outside surface of bushing plate through using selecteed thermotolerance material to the outside surface of bushing plate; Even the continuous glass fibre manufacturing of under the condition of high temperature, being exposed to the sun for a long time with bushing in, also can keep stable status and performance for a long time.
Used the area of the overlay film of any one above material in the above-mentioned materials group for the formation of the outside surface of bushing plate; But it is comprehensive necessarily to cover it; Preferably cover and remove outside the periphery and end face of nozzle, the main position more than 1/5 in the area that exposes face of the outside of bushing plate is regional.In addition, the part that is capped may not be the successive face, and may not concentrate on a position, if only cover suitable position, preferably covers a plurality of positions, then can cover the position of evaporation especially easily expeditiously.Here; Above-mentioned " more than 1/5 main position zone " be meant, satisfy the outside surface that forms the condition of high temperature especially easily or because of tension etc. make its at the more weak outside surface of textural intensity, or be judged as the outside surface of any condition in the most violent outside surface of evaporation.Such outside surface both can be obtained through dummy model, also can utilize actual measurements such as temperature survey to obtain.
Here, with respect to the structure of setting up of bushing plate,, then it there is not special qualification for the material of the material of bushing plate, nozzle and nozzle so long as have the structure of continuously and stably extracting the melten glass that is in the condition of high temperature out.In addition, there be not special limiting for the method that the covering material that is formed more than one materials in pottery, glass-ceramic or the glass is constructed yet.
In addition, face shaping and the size for nozzle, bushing plate do not have special qualification yet.For example; Can adopt drum, polygon barrel shape, the profile of the truncated cone (frustum) shape or the shapes such as profile of domed for nozzle form; Also can be at its outside surface by predetermined distance or the groove of regulation, concavo-convex, dimple or projection etc. are set at random, so as to form easily with used ceramic, glass-ceramic or glass in the different overlay film of overlay film of more than one materials.In addition, also can utilize various medicine processing such as physical means such as sandblast or soda acid etc. that the condition of surface of its outside surface is formed the condition of surface with trickle fluctuating.In addition, also may not be plane for the bushing plate, for example also can adopt the state of having implemented concavo-convex or groove etc., also can adopt with the bushing slab integral crooked state.
For the equipping position of many nozzles of bushing plate, even the structure that each nozzle is provided in the optional position each other also has no relations.For example; As the constituent parts configuration of many nozzles, both can be to be configured to three nozzle locations to form leg-of-mutton position, also can be to be configured to the position that four nozzle locations roughly form rectangular shape; And the two combined location, the position of adopting diverse other configurations.
In addition; Above-mentioned structure is at the as above above-mentioned structure that has applied suitable material on the outside surface of the periphery of nozzle and the bushing plate the end face, and still, this is not periphery and an end face of having a mind to get rid of nozzle; For example; For the periphery and end face of nozzle, if can fully avoid to the influence of quilt with the spun glass of molten state extraction, and; On such position, form overlay film and can further bring effect, then also might as well be able to form overlay film with above-mentioned overlay film unlike material.Yet, under the situation that forms such overlay film, be preferably in and think and avoid forming such overlay film when peeling off easily.
On the other hand; Bushing is used in the continuous glass fibre manufacturing that the present invention relates to; Used the position of the overlay film of any the above material in pottery, glass-ceramic or the glass as formation; Except the outside surface of bushing plate, also can with as the outside surface of the bushing surrounding wall portion of the integrant of bushing main body as object.In this case, both can on the whole zone of the outside surface of bushing surrounding wall portion, form above-mentioned overlay film, perhaps also can be at suitable regional area, for example with regional area that the bushing plate links to each other on the above-mentioned overlay film of formation.Here; For example also can form overlay film on the surface of the strengthening part of construction portions such as cooling tube or fan, terminal (terminal), bushing plate etc.; But; The overlay film that forms at such position both can be the overlay film with the structure of the identical material of outside surface of bushing plate, thickness etc., also can be the overlay film of different structure.
In addition; For the formation method of overlay film; If forming the position of overlay film only is the position that is specially limited, then for the position that does not form overlay film, also can be at the state that utilizes organic materials, other mask material to cover this outside surface in advance formation overlay film down; Afterwards, utilize the method for regulation to remove mask and optionally form the state of overlay film.Perhaps, also can carry out the assembling procedure of the regulation of bushing plate as required in advance, the way only forms overlay film on the parts of regulation therein.
On the other hand; For the continuous glass fibre manufacturing that the present invention relates to for bushing, if the bushing plate is made up of platinum alloy or platinum, then except high heat resistance; Also can with the high temperature of melten glass under be difficult to keep higher performance aspect the reaction; Therefore not only the outside surface of bushing plate but also the time dependent that can reduce internal surface change, because the deterioration of internal surface is less, so can produce continuous glass fibre expeditiously.
Here; The bushing plate is to be meant by what platinum alloy or platinum constituted; The material that constitutes the bushing plate also can be to contain rhodium, iridium, yttrium, ruthenium, palladium, osmium, titanium, gold, molybdenum, tungsten, magnesium, calcium, hafnium or zirconium etc. in right amount except platinum is platinum, for the content of these coexistence compositions; If can realize regularity abilities such as thermotolerance, then not have special qualification.Certainly, in order to realize that required effect also can be also with the material beyond platinum alloy and the platinum.In addition, as the material of the bushing plate that the present invention relates to, what adopt platinum alloy may not only be the alloy of solid solution state, also can be that microparticulate is in platinum or add ceramic member and the material of fixed sintering metal shape.
In addition; Bushing is used in the continuous glass fibre manufacturing that the present invention relates to; If overlay film is multi-ply construction; Through each rerum natura such as the coefficient of expansion or thermotolerance is adjusted in the scope of regulation, can selects respectively easily and the corresponding material in interface of outside surface and bushing plate (perhaps in addition bushing surrounding wall portion), thereby can constitute the optimum configuration of bushing plate requirement.
Here, overlay film is that multi-ply construction is meant that overlay film constitutes two-layer above layer state through the construction of film forming repeatedly.
For the gauge of each layer of the overlay film that constitutes multi-ply construction, composition etc., can select to form preferred composition, structure (wherein, being limited to more than one materials that used in pottery, glass-ceramic or the glass) as required.In addition, each layer need not evenly, both can be that oblique structure also can be the pinprick structure.In addition, also can in the stratified composition of structure, add aggregate arbitrarily wittingly.As aggregate, can use at preferred aggregates in aspect such as thermotolerance, the coefficient of expansion or reactivities.For example, can use glass filler, ceramic packing, glass-ceramic filler, precious metal filler etc. in right amount.In addition, can select random shape for the shape of filler.For example, can use roughly fibrous, roughly cotton-shaped, roughly latticed, roughly braid shape, roughly cryptomere, roughly coccoid, roughly broken thing shape, roughly porous insert shape, roughly polyhedral, roughly cylindric, roughly polygon prism shape, roughly tabular, roughly particulate state, roughly coniform, roughly polygonal pushing away (polygonal pushing away) shape or roughly alphabetical font column etc.
In addition, when overlay film is multi-ply construction, give distinctive performance, can realize more high-performance each layer.For example; Also can be on bushing plate surface, to dispose with the layer that engages with drain board material such as platinum alloy or platinum as emphasis; Utilize the fine and close layer of upper-layer configured of this layer; Inhibition is from the evaporation of bushing plate, and also can be the layer that configuration itself has dense construction on bushing plate surface, and layer adopts and do not allow the high layer of caducous thermotolerance above that.In addition; For example; Also can adopt like the configuration thermal expansivity layer that such configuration added specific fillers that gradually changes and suppress to take place crackle, and then layer has a stable on heating while and prevents the precious metal filler from the evaporation that kind on bushing plate surface efficiently above that.
In addition, the heat resisting temperature of overlay film depends on the kind of constructional method and construction material, need have the thermotolerance more than at least 800 ℃, more preferably has the thermotolerance more than 1000 ℃, further preferably has the thermotolerance more than 1200 ℃.In order to realize such thermotolerance, preferably burn till with this temperature more than temperature.
In addition; Bushing is used in the continuous glass fibre manufacturing that the present invention relates to; If its overlay film is in prefabricated overlay film, spraying overlay film, the immersion film-coated and vapor-deposited film any; Then can form optimum configuration, can implement cheapness and the high overlay film of quality economically through the overlay film of selecting to be complementary with the bushing panel material.
Here; Overlay film is that in prefabricated overlay film, spraying overlay film, the immersion film-coated and vapor-deposited film any is meant; Except nozzle periphery and nozzle face, the overlay film of implementing at the outside surface of bushing plate forms through prefabricated overlay film in advance, perhaps uses decompressor and injection moulding forms; Perhaps formed, perhaps adopted the vapour deposition method of physics or chemistry to form having adjusted being used dipping in the slurry of bushing plate in advance by the dipping of construction surface.
For these film formation methods, it both can adopt a method, also can and use a plurality of methods.In addition, the combination for these methods and other film formation method also has no problem.
In addition, the continuous glass fibre manufacturing installation that the present invention relates to is used bushing, except that above-mentioned, if the thickness of preferred overlay film below 1mm, then can form the overlay film of long-time stable structure.
Here, the thickness of overlay film is meant below 1mm, measures the thickness of overlay film when construction or after the construction, and the observed value at the thickest thick position is as below the 1mm.
The gauge control of overlay film the reasons are as follows below 1mm is said.First reason is: if the thickness of film surpasses 1mm, the dried of construction surface and overlay film taken place easily peel off.As stated, the bushing plate is made up of platinum alloy or platinum, if consider the manufacturing cost of continuous glass fibre manufacturing with bushing, then the thickness of platinum alloy or platinum manufactures below the 2mm.Except the continuous glass fibre manufacturing with the nozzle periphery of bushing and the bushing plate outside surface the end face; By having used the overlay film more than in pottery, glass-ceramic and the glass material group any to apply; If the thickness of the overlay film of the desciccator diaphragm of this overlay film more than 1mm, then forms the hard desciccator diaphragm that is difficult for deforming.Consequently, as the platinum alloy or the platinum of construction surface, when some distortion took place in construction, desciccator diaphragm can not followed this distortion, causes peel off dangerous higher.In addition, be during hard desciccator diaphragm more than burning till 1mm, contraction to have taken place to burn till as second reason.If the lower film of density also can suppress to burn till contraction, if prevent the evaporable film of platinum, the film that then must have higher density.The density of film can be judged through measuring porosity.If porosity more than 10%, then is difficult to suppress the platinum volatilization, preferably need be below 5%.Increase if improve density then burn till to shrink, increase if the danger of the be full of cracks of film etc. more than 1mm, takes place when then burning till thickness.Thereby, the gauge of overlay film as the whole thickness of layer preferably below 1mm, more preferably below 800 μ m, further preferably below 600 μ m, most preferably below 400 μ m.
Even can utilize the continuous glass fibre manufacturing that the present invention relates to is the continuous glass fibre of the glass material of known that kind with the continuous glass fibre of bushing manufacturing, it also can be made.For example; Can adopt E glass (non-alkali glass composition), AR glass (alkali resistant glass composition), C glass (containing acid proof soda-lime glass forms), D glass (realizing the composition of low-k), S glass (realizing the composition of HS, snappiness rate), T glass (realizing the composition of HS, snappiness rate) and H glass (realizing the composition of high-k) or M glass, the such glass material of L glass, other material also has no relations in addition.
On the other hand, continuous glass fibre manufacturing of the present invention has with the method for manufacture of bushing: the bushing main body forms operation, and its assembling comprises the bushing main body of bushing surrounding wall portion, bushing plate and a plurality of nozzles; Apply operation, it forms overlay film at the outside surface of the bushing plate of the bushing main body of having assembled at least; Firing process, it forms dense construction with formed overlay film heating, and this method of manufacture is to make the method for manufacture of above-mentioned each described continuous glass fibre manufacturing with bushing.
Form operation for the bushing main body; In order to form the essential structure of above-mentioned continuous glass fibre manufacturing with bushing; As long as be assembled with bushing surrounding wall portion, bushing plate and a plurality of nozzle, for assembling sequence, be preferably set to and make high-quality structure with optimum efficiency.For example, both can be preferentially the bushing plate to be set up whole nozzles, opposite with it, also can be to set up nozzle at last.As the method for setting up of nozzle, also can adopt known various method.
In addition; For at least (promptly at the bushing plate of the bushing main body of having assembled; Only be bushing plate or bushing plate and bushing surrounding wall portion) outside surface form the coating operation of overlay film, as long as can utilize above-mentioned various methods, the bushing that constitutes stabilised quality gets final product.
For for the firing process that formed overlay film is added the thermosetting dense construction; The state that has abundant weather resistance in order under the temperature of utilizing the continuous glass fibre manufacturing with bushing extraction spun glass, overlay film to be in; Through the temperature that overlay film heating is drawn out of until spun glass, thereby can form the state of overlay film and the surperficial firm engagement of bushing.
The heating unit that in firing process, carries out; Both can be to use partial heating arrangements, also can be the mechanism that has adopted the whole heating of bushing, in addition; It also can be the mechanism that in electric furnace, various fuel-based process furnace, keeps proper temperature; Also have, also can the continuous glass fibre manufacturing be provided in after the glass melting furnace with bushing, utilize the heating source of glass melting furnace to heat.
For the Heating temperature in the firing process, it is preferably at 1100 ℃～1500 ℃ scope internal heating.This is because when bushing use in heating continuous glass fibre manufacturing under than 1100 ℃ of low temperature, exists the globality heating to be in inhomogeneous state, perhaps produces the danger of the problem of the position that kind that does not have even heating, so it is not preferred.In addition, opposite with it, if heating above under 1500 ℃ the temperature, then overlay film is endowed and forms overladen heat energy, consequently, sometimes can shorten the life expectancy of overlay film, so also not preferred.According to above-mentioned viewpoint, in order to obtain the more overlay film of stabilised quality, the scope that the Heating temperature in the firing process is more preferably 1200 ℃～1400 ℃.
In addition, the continuous glass fibre manufacturing installation that the present invention relates to is characterized in that, constitutes: use above-mentioned any continuous glass fibre manufacturing to use bushing, to carry out the spinning of continuous glass fibre.
Utilize the form of the continuous glass fibre goods of the spun glass (continuous glass fibre) that this continuous glass fibre manufacturing installation makes for use, do not have special qualification.That is, can be yarn, rove, DWR (directly roving wind (direct windingroving), chopped strand, milled fibre (milled fiber), fabric, mat (mat), band (tape) or weave cotton cloth etc., as the form of fiberglass products.
Here, in this continuous glass fibre manufacturing installation, can be except that above-mentioned suitably and establish various attendant equipments or anchor clamps etc.For example, can be the cooling of spun glass with the such refrigerating unit of pipe windburn fan, have a mind to adjust the device of the redox condition of bushing panel area, the cooling medium dissemination apparatus of cooling usefulness, the temperature control equipment of bushing plate etc.Both can use separately, also can and with these the device, can not hinder the use of other devices.
On the other hand, the method for manufacture of the continuous glass fibre that the present invention relates to is characterized in that, uses above-mentioned continuous glass fibre manufacturing installation, Yi Bian keep watch on the outside surface and the spinning situation of bushing plate, uses continuous glass fibre Yi Bian make matrix material.
To being used to use above-mentioned continuous glass fibre manufacturing installation; The outside surface and the spinning situation of keeping watch on the bushing plate on one side; Making matrix material on one side narrates with the object lesson of continuous glass fibre; Through the continuous glass fibre manufacturing installation being equipped on the glass melting furnace that melten glass is fused of the condition of high temperature, will importing in the continuous glass fibre manufacturing installation from the effusive melten glass of glass melting furnace, and then release continuously when making spun glass from the nozzle of the bushing plate that is attached to the continuous glass fibre manufacturing installation; Keep watch on one side and whether spun glass is successfully extracted out and good spinning to bushing plate outside, Yi Bian make.This also can observe the bushing plate in the sight glass fiber, tackles any situation if desired, and for example, outside surface adheres to foreign matter to be produced, fragile position etc. takes place, and can carry out its required treatment for correcting as early as possible.
Here, the method for the spinning situation of the outside surface of keeping watch on the bushing plate and continuous glass fibre can adopt the whole bag of tricks.For example; Can be via the image capturing apparatus of the solid-state image pickup that has carried pick up tube, CCD or CMOS etc.; Utilize wired or wireless Intranet circuit to outside surface and the moving image of the situation of spinning or device transmission information and the supervision that discontinuous rest image writes down with numeral or analog image form with the bushing plate; In addition; Also can utilize visible rays and dimensional change and temperature variation non-image or the regulation position that other electromagnetic electronic recording system sequential test should be noted that, this value is stored on the indicating meter and recording paper or recording medium, and keep watch on via visual or monitor program supervision etc.
In addition; The method of manufacture of the continuous glass fibre that the present invention relates to; If above-mentioned matrix material is used for any of FRP, FRTP and GRC with continuous glass fibre, can be from the continuous glass fibre goods of the high-quality manufacturing of secular manufacturing of production initial stage and each purposes coupling.Make efficient through improving, can reduce production cost.
At this moment; If matrix material is used for any of FRP, FRTP and GRC with continuous glass fibre, then matrix material can be used as with continuous glass fibre and constitutes thermosetting resin and strengthen the continuous glass fibre goods that body (also being called fibre reinforced plastics), thermal softening property hardening of resin body (fibreglass reinforced thermoplastic) or alkali-resistant glass fiber are strengthened cement products (also being called glass fibre reinforced composion (ジ one ア one Le シ one)).
Constituting under the situation of these matrix materials with continuous glass fibre; For selecting, what forms with the formation beyond the spun glass with blending ratio, the blending means of spun glass and the matrix material that the present invention relates to as the matrix material that the present invention relates to; So long as can realize performance that physical strength, chemical durability or thermotolerance, resistance to chemical reagents or weathering resistance etc. are required, can add any thing.
In addition, in the method for manufacture of the continuous glass fibre that the present invention relates to, can utilize the whole bag of tricks to the various surface-coated agent of the surface coated of the spun glass under the bushing.For example; Can be applied that collecting agent, charged preventor, interfacial agent, coincidence begin agent, overlap suppressor factor, antioxidant, overlay film form agent, coupler or lubricant, also can sneak into water reducer, flowing agent, tackifier, water-resisting agent, rust-preventive agent, hardening accelerator, sclerosis delayer, slag, flyash, silicon smog (シ リ カ ヒ ユ one system), tinting material or accelerating chemicals etc. as required.
Here, the spun glass of making in the method for manufacture of the continuous glass fibre that the present invention relates to does not have special qualification for Fibre diameter, the fibre section shape of the monofilament that constitutes single thread.That is, can use the spun glass of the monofilament of a few μ of diameter m to tens μ m, and then, circle, perhaps essentially rectangular etc. of ellipse, flat circle, hollow circle roughly just also can suitably be adopted for cross-sectional shape.
In addition, the fiberglass products of making in the method for manufacture of the continuous glass fibre that the present invention relates to particularly, for example, can use in following various purposes.For example; It is in the purposes of vehicle-mounted association; Have enclose before car body roof (hood), window frame, the car body, compartment, lamp housing, air ducting, splash pan fence, fuel tank, ventilator, water tank, dirt box, seat, preceding wind-guiding cone, splash pan fence, curtain, strainer, tracheae, muffler filter device, instrument panel, fan blade, scatterer, tire or correct time cingulum etc.; In the related purposes of electronics; Have casting of electronic device material, gear tep reel, various shell, used for optical part container, the electronics taken in container, switching box or insulating supporting body etc.; In the related purposes of air equipment; Have engine shield, air flue, sealing membrane, freight container, curtain, interior trim spare, toilet, tire, vibrationproof part or correct time cingulum etc.; In related purposes is transported in shipbuilding, land transportation by sea; Have motor dory, speedboat, fishing boat, spat (De one system), safety buoy, marine freight container, buoy, oil tank, teleseme, pavement marker, deviation mirror, freight container, tray, guardrail, head light guard shield or spark screening glass etc.; In construction, building, the related purposes of building materials; Have assembly between bathtub, sanitation of bath-room, bedpan, purification tank, water tank, interior dress plate, capsule, valve, handle, wall reinforcement, precast concrete plate, flat board, ripple plate, tent, window shutter, adorn plate, sash, pipe arrangement flexible pipe, water reservoir, swimming pool, road, structure sidewall, concrete frame, waterproof canvas, the lining that discharges water, health film or fly net etc. outward; In the related purposes of agricultural; Have plastic greenhouse, vertical storage tank, fog nozzle, pillar, lining or soil improvement agent etc.; In the related purposes of industrial plants; Have sack cleaner, sewer pipe, water purification relative unit, anti-vibration concrete stiffener (CRG), catch basin, band, medicine groove, reactive tank, container, fan, pipeline, anti-corrosion lining, valve, refrigerator chamber, dish, reach in freezer, groove, equipment unit, motor boot, insulated wire, transformer insulated layer, cable, working suit, curtain, evaporation plate or apparatus casing etc., in the related purposes of leisure physical culture, have fishing rod, ski, archery, golf club, swimming pool, paddle, surfboard, picture frame, the helmet, shield, flowerpot or display panel etc.; In the related purposes of daily necessities, have desk, chair, bed, bench, phantom, rubbish container or mobile termination guard member etc.
In addition, the method for manufacture of the continuous glass fibre that the present invention relates to is characterized in that, the supervision of spinning situation is that above method realizes among arbitrary in the measurement of measurement and Fibre diameter of shooting, spinning speed according to spinning.
According to such structure; Can utilize any the investigation the measurement of Fibre diameter of speed that the shooting, this spun glass of image of state of the outside surface of the spun glass that expression extracts out with the nozzle of bushing from the continuous glass fibre manufacturing continuously extract out from nozzle and each continuous glass fibre, carry out the supervision of spinning situation.
Photography for the spinning image; A plurality of glass fiber bundles of both can having made a video recording simultaneously; Also can utilize of the monofilament shooting of each camera head respectively to the regulation radical; As long as,, can select optimum condition according to imaging environment and picture pick-up device for its sharpness, shooting frequency etc. for the information that shooting can obtain to stipulate.
(1) as stated; Bushing is used in the continuous glass fibre manufacturing that the present invention relates to; Many nozzles that constitute through being attached to the bushing plate form continuous glass fibre (glass strand) so that melten glass flows out, and are being formed with overlay film except the periphery of said nozzle and the outside surface of the above-mentioned bushing plate the end face (outside surface that according to circumstances also comprises the bushing surrounding wall portion), and this overlay film has used the material more than in pottery, glass-ceramic and the glass material group any; Therefore; In making the process of continuous glass fibre, the generating capacity of the evaporant that can suppress to take place from the outside surface of bushing, and; Because bushing is by firm enhanced structure, so can in the manufacturing of the spun glass that is used for various uses, realize high productivity.
(2) in addition; If the continuous glass fibre manufacturing that the present invention relates to is made up of platinum alloy or platinum with bushing; Then since form thermotolerance high, be difficult to take place the structure of size distortion etc. for a long time, so can make high-precision glass with high dimension stability.
(3) in addition; If the continuous glass fibre manufacturing that the present invention relates to is multi-ply construction with the overlay film of bushing; Then each layer structure of overlay film can bear the desired various performances of outside surface of bushing, can relax the desired performance of each layer, forms stable layer structure easily.
(4) in addition; If the continuous glass fibre manufacturing that the present invention relates to is among arbitrary in prefabricated overlay film, spraying overlay film, the immersion film-coated and vapor-deposited film with the overlay film of bushing, then can utilize the film formation method with the structure of bushing plate, size, its condition of surface coupling to form best overlay film.In addition, can select coating process according to the kind of overlay film.
(5) in addition, if continuous glass fibre manufacturing of the present invention with the thickness of bushing below 1mm, then since form overlay film be difficult to generation of cracks or peel off and with the incorporate firm structure of bushing plate, so can life-time service.
(5) continuous glass fibre manufacturing of the present invention has with the method for manufacture of bushing: the bushing main body forms operation, and its assembling comprises said bushing surrounding wall portion, bushing plate and the many bushing main bodys that nozzle forms; Apply operation, it forms overlay film at the outside surface of the bushing plate of the bushing main body of having assembled at least; Firing process; It heats the overlay film that forms to form dense construction; Therefore; Can form the state that fine and close overlay film and continuous glass fibre manufacturing are connected with the outside surface of bushing owing to form the structure that can suppress reliably from the evaporation of the outside surface of bushing, so can obtain to realize dimensional stability raising, suppress the continuous glass fibre manufacturing that the glass quality of foreign matter generation etc. improves and use bushing.
(7) continuous glass fibre manufacturing of the present invention constitutes with device and uses above-mentioned continuous glass fibre manufacturing to use bushing, carries out the spinning of continuous glass fibre, so can obtain superior in quality various continuous glass fibre goods.
(8) method of manufacture of continuous glass fibre of the present invention is used above-mentioned continuous glass fibre manufacturing installation; The outside surface and the spinning situation of keeping watch on the bushing plate on one side; Making matrix material uses continuous glass fibre on one side; So can keep stable high efficiency production continuously, can make the defective that the continuous glass fibre goods take place be suppressed at bottom line with resulting from foreign matter etc.
(9) in addition; The method of manufacture of continuous glass fibre of the present invention; If matrix material is used for any of FRP, FRTP and GRC with continuous glass fibre, then can be superior in quality and the fiberglass reinforced articles of the desired various uses of smooth supply the market that has no to lag behind.
(10) method of manufacture of continuous glass fibre of the present invention; If the supervision of spinning situation is to carry out according to the mode more than in the measurement of the measurement of the shooting of spinning image, spinning speed and Fibre diameter any; Then obtain the information of corresponding as the various problems that can inferior limit suppress to take place when glass is made easily; Implement suitable reply as early as possible, can keep the quality of the spun glass of the state that is in stable quality for a long time.
Description of drawings
Fig. 1 is the stereographic map of the embodiment of the bushing that possessed of expression continuous glass fibre manufacturing installation of the present invention.
Fig. 2 is the vertical view of the embodiment of the bushing that possessed of expression continuous glass fibre manufacturing installation of the present invention.
Fig. 3 is that the major portion of the embodiment of the bushing that possessed of expression continuous glass fibre manufacturing installation of the present invention is amplified the vertical profile front view.
The drawing reference numeral explanation:
Bushing is used in 1 continuous glass fibre manufacturing
2 bushing main bodys
3 bushing surrounding wall portion
4 bushing plates
5 melten glass are supplied with the space
6 nozzles
7 overlay films
The G melten glass
F continuous glass fibre (glass strand)
Embodiment
Below, with reference to description of drawings continuous glass fibre manufacturing of the present invention with bushing (below, abbreviate " bushing " as).
Fig. 1～Fig. 3 is the figure of the bushing 1 that possessed of expression continuous glass fibre manufacturing installation; Fig. 1 is the stereographic map of the major portion of expression bushing 1; Fig. 2 is the vertical view of the major portion of expression bushing 1, and Fig. 3 is an amplification vertical profile front view of only representing the nozzle periphery of bushing 1.As depicted in figs. 1 and 2, this bushing 1 is the bushing that when shaping is used for continuous glass fibre (or spinning) that the E glass of FRP forms, uses.And the bushing main body 2 of this bushing 1 is fixed with bushing plate 4 in the bottom of bushing surrounding wall portion 3 and constitutes, and its inside is that melten glass is supplied with space 5 (with reference to Fig. 3).Particularly, bushing plate 4 is platinum rhodium systems of shape in the form of a substantially rectangular, set up 200 in its bottom surface and have stable on heating nozzle 6, and the peripheral end face of bushing plate 4 utilizes the TIG welding and engages with the bottom inner peripheral surface of bushing surrounding wall portion 3.
And, on the outside surface of the outside surface of bushing plate 4 and bushing surrounding wall portion 3, and be equivalent on 2/5ths the part of its total area (among Fig. 1 and Fig. 2 mark cross hatch) and be formed with the double-deck overlay film 7 that constitutes.The overlay film 7 that this bilayer constitutes has 1300 ℃ thermotolerance; Being configured to of tight zone that is equivalent to the first layer; Silicon powder, aluminium powder in the non-alkali glass powder constituent, have been mixed; And can cut off the tight zone structure from the evaporation of the platinum of bushing plate 4 and rhodium as far as possible expeditiously, its gauge is 200 μ m.In addition, the heat-resistance high-strength degree layer that is equivalent to the second layer of overlay film 7 is the compound structure layer that contains ceramic fiber and contain the non-alkali glass powder, and its gauge is 100 μ m.This heat-resistance high-strength degree layer is engaged the crackle that can suppress the overlay film surface.And, be implemented in overlay film 7 that the bilayer on this bushing plate constitutes and have the thickness that the first layer and the second layer add up to 300 μ m.
For the position of the overlay film 7 that forms double-layer structural; Avoid the near zone of the nozzle 6 in the outside surface of the end face of the nozzle 6 of platinum rhodium system and its periphery and bushing plate 4; Particularly; Till from the position suitable to the position of getting the size more than the 1mm, avoid forming overlay film 7, formation overlay film 7 on the prescribed position of the outside surface of the outside surface of the bushing plate 4 beyond it and bushing surrounding wall portion 3 with the boundary with nozzle 6 of the outside surface of bushing plate 4.Adopt the formation form of such overlay film 7; This is because known through investigation therebetween; Evaporant from these positions is accumulated near nozzle 6 through fan around the bushing plate 4 (omitting diagram) and cooling tube (omitting diagram) cooling; Like this, just the shaping to spun glass F causes detrimentally affect.In addition; End face if this is at the front end of nozzle 6 forms overlay film 7; Though problem does not take place in the manufacturing initial stage; But in the manufacturing of long glass continuous fibre F, any reason all can make the part of overlay film 7 be attached on the glass continuous fibre F, therefore can make spun glass F that the danger of fracture of wire takes place.
And the overlay film of the first layer in the overlay film 7 utilizes the masking belt of organic membrane etc. that the position of not implementing this overlay film is sheltered, and utilizes spray-coating afterwards and forms, and for the second layer, forms through using atomizer spray from the top of the first layer.
Manufacturing sequence for the bushing that forms by above-mentioned structure 1; At first; The bushing plate 4 and bushing surrounding wall portion 3 of nozzle 6 have been set up in advance via welding; The bushing main body of assembling bushing main body 2 forms after the operation, carries out 2/5ths the part that overlay film 7 is formed on the total area of the outside surface that is equivalent to bushing plate 4 and bushing surrounding wall portion 3, so that on this bushing main body 2, form the coating operation of above-mentioned double-layer structural.Next; To be in the bushing 1 that has formed these overlay film 7 states is assembled into after the continuous glass fibre manufacturing installation; Through using the incidental heating unit of continuous glass fibre manufacturing installation bushing 1 to be heated to equably 1300 ℃ the condition of high temperature; Via being used to improve the overlay film 7 whole densification and the firing process of cementability, thereby the overlay film that can obtain to have high stability is constructed.
The method of the continuous glass fibre that the E glass that uses the continuous glass fibre manufacturing installation possess the bushing 10 that is formed by above-mentioned structure to make the FRP purposes is formed then, is described.
At first, use raw material to drop into machine and will be mixed into the frit input glass melting furnace that E glass is formed.The frit that drops into like this, the heating source that in the glass melting groove, is utilized electricity or fuel etc. is heated to more than 1300 ℃, and the vitrifying reaction takes place, and forms the melten glass that is involved in inhomogeneous thick molten states such as a large amount of reactive bubbles.Be adjusted to the melten glass G of homogeneous state through homogenize melten glass that operation will this thick molten state of clarification or stirring etc. a series of; Afterwards; The melten glass G of this homogeneous supplies with space 5 to the melten glass of bushing 1 and flows into through the forebay of glass melting furnace.
Then; Melten glass to bushing 1 is supplied with the melten glass G that flows in the space 5; After being trapped in the melten glass supply space 5; From 2000 open pores with front end of stable on heating nozzle 6 setting up at the bushing plate 4 that utilizes heating unit etc. to be adjusted to proper temperature, melten glass is interruptedly extracted out with thread continuously and not, thereby forms the glass strand F of diameter from a few μ m to tens μ m.Here; For the spinning situation (shaping situation) of the glass strand F under the nozzle 6 and the outside surface situation of bushing plate 4; Except periodicity ground by full-time surveillant's visual surveillance; Also constitute, utilize the part shooting of ccd video camera, and utilize the LAN (local area network) in the factory to keep watch on this photographed images as required at other monitoring room to its situation.Through such supervision system, can be corresponding one by one when any problem has taken place F at the glass strand of extracting out continuously (glass monofilament).In addition, can write down image as required, and then can when carrying out high-quality shaping, play a role from the reflection of ccd video camera.
Glass strand F from nozzle 6 extractions; Utilize nozzle 6 under cooling fan and cooling tube; Make its rapid cooling, have the sufficient spun glass of E glass, at the various collecting agents of its surface coated silane coupling agent or starch etc. with formation; To form, it is batched the state that is called pancake (cake) (also being called the coarse sand volume) or cheese (cheese) in paper tube with formation with tens or the precursor of the state of several thousand boundlings.
Then, utilize the continuous glass fibre manufacturing installation, can as required continuous glass fibre further be processed into various continuous glass fibre goods.For example,, many precursor are alleviated from dried a plurality of pancakes making under the situation of glass roving, on one side the place to go twill draw on one side together, the wind2 that use has a winding machine batches and manufactures backrush body (also being called roller, perhaps the rollback body) shape.
As stated; Possess the continuous glass fibre manufacturing installation of bushing 1 in use and make under the situation of spun glass of various uses, can suppress evaporation efficiently, and then bushing plate 4 self also can be kept HS from bushing plate 4; Therefore; The life expectancy of continuous glass fibre manufacturing installation is than increase in the past, and high efficiency production is achieved, and has the various continuous glass fibres that stable performance and superior in quality matrix material are used thereby can make.
Utilizability on the industry
Bushing that the present invention relates to and continuous glass fibre manufacturing installation and the method for manufacture that has adopted the continuous glass fibre of this device; Except the matrix material purposes of making FRP etc.; Can also be applied to make the continuous glass fibre of other purposes, can be applied in the extensive fields.In addition, so long as use the manufacturing installation of the same form of the continuous glass fibre manufacturing installation that the present invention relates to make, even other glass material also can use the present invention.
Claims (11)
1. bushing is used in a continuous glass fibre manufacturing; It is that bushing is used in the continuous glass fibre shaping that is described below; Inside has melten glass and supplies with spatial bushing main body; Possess the bushing surrounding wall portion and be equipped on the bushing plate of the bottom of this bushing surrounding wall portion, and set up to make at the bottom surface side of said bushing plate and supply with the spatial melten glass from said melten glass and flow out a plurality of nozzles with the shaping continuous glass fibre
Said continuous glass fibre manufacturing is characterised in that with bushing,
Periphery and end face at said nozzle do not form overlay film; And the nozzle near zone till leave the position more than the 1mm with outside surface suitable with boundary nozzle the position of said bushing plate does not form said overlay film; And the zone beyond the said nozzle near zone of the outside surface of said bushing plate is formed with said overlay film, and said overlay film has used any the above material in pottery, glass-ceramic and the glass material group.
2. bushing is used in continuous glass fibre manufacturing as claimed in claim 1, it is characterized in that,
Outside surface in said bushing surrounding wall portion is formed with said overlay film.
3. bushing is used in continuous glass fibre manufacturing as claimed in claim 1, it is characterized in that,
Said bushing plate is made up of platinum alloy or platinum.
4. use bushing like each described continuous glass fibre manufacturing in the claim 1～3, it is characterized in that,
Said overlay film is multi-ply construction.
5. use bushing like each described continuous glass fibre manufacturing in the claim 1～3, it is characterized in that,
Said overlay film is any in prefabricated overlay film, spraying overlay film, the immersion film-coated and vapor deposition overlay film.
6. use bushing like each described continuous glass fibre manufacturing in the claim 1～3, it is characterized in that,
The thickness of said overlay film is below 1mm.
7. a continuous glass fibre manufacturing is with the method for manufacture of bushing, and it is to make in the claim 1～6 each described continuous glass fibre manufacturing with the method for manufacture of bushing,
Said continuous glass fibre manufacturing is characterised in that to have with the method for manufacture of bushing:
The bushing main body forms operation, and its assembling comprises the bushing main body of said bushing surrounding wall portion, bushing plate and a plurality of nozzles; Apply operation, it forms overlay film at the outside surface of the bushing plate of the bushing main body of having assembled at least; Firing process, it forms dense construction with formed overlay film heating.
8. a continuous glass fibre manufacturing installation is characterized in that,
Constitute: bushing is used in each described continuous glass fibre manufacturing in the use claim 1～6, to carry out the spinning of continuous glass fibre.
9. the method for manufacture of a continuous glass fibre is characterized in that,
Use the described continuous glass fibre manufacturing installation of claim 8,, use continuous glass fibre Yi Bian make matrix material Yi Bian keep watch on the spinning situation of the outside surface and the continuous glass fibre of bushing plate.
10. the method for manufacture of continuous glass fibre as claimed in claim 9 is characterized in that,
Said matrix material is used for any of FRP, FRTP and GRC with continuous glass fibre.
11. the method for manufacture like claim 9 or 10 described continuous glass fibres is characterized in that,
The supervision of said spinning situation is to realize through the method more than in the measurement of the measurement of the shooting of spinning image, spinning speed and Fibre diameter any.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP226458/2006 | 2006-08-23 | ||
| JP2006226458 | 2006-08-23 | ||
| PCT/JP2007/065956 WO2008023627A1 (en) | 2006-08-23 | 2007-08-16 | Bushing for the production of glass continuous filaments, process for production of the bushing, equipment for producing glass continuous filaments and process for the production of the filaments with the equipment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101506113A CN101506113A (en) | 2009-08-12 |
| CN101506113B true CN101506113B (en) | 2012-09-19 |
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ID=39106712
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800313023A Active CN101506113B (en) | 2006-08-23 | 2007-08-16 | Bushing for production of glass continuous filament and manufacture method thereof, equipment for producing glass continuous filament and process for production of the filament using the equipment |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5403291B2 (en) |
| CN (1) | CN101506113B (en) |
| TW (1) | TW200812926A (en) |
| WO (1) | WO2008023627A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967313B (en) * | 2010-11-03 | 2012-11-21 | 重庆国际复合材料有限公司 | Protective coating for inhibiting platinum bushing from being oxidized and volatilized, and manufacturing method and application thereof |
| CN102030469B (en) * | 2010-11-16 | 2013-08-07 | 重庆国际复合材料有限公司 | Glass melt adhesion-preventing method for discharge plates |
| CN102676972A (en) * | 2012-05-30 | 2012-09-19 | 重庆国际复合材料有限公司 | Treatment method for platinum rhodium bushing |
| CN103524033A (en) * | 2012-07-06 | 2014-01-22 | 苏州宏久航空防热材料科技有限公司 | High-temperature alloy bushing plate plated by platinum and alloy thereof, and preparation method of high-temperature alloy bushing plate |
| CN106283223B (en) * | 2015-05-18 | 2019-10-01 | 吉林化纤股份有限公司 | Spinning head used in the preparation method and preparation process of flat viscose filament yarn |
| JP2020040850A (en) * | 2018-09-07 | 2020-03-19 | 田中貴金属工業株式会社 | Bushing for manufacturing glass fiber |
| JP6624750B1 (en) * | 2018-09-07 | 2019-12-25 | 田中貴金属工業株式会社 | Bushings for glass fiber production |
| JP2023514479A (en) * | 2019-12-20 | 2023-04-06 | クックソン プレシャス メタルズ リミティド | Chip plate and corresponding bushing |
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|---|---|---|---|---|
| US4846865A (en) * | 1988-03-15 | 1989-07-11 | Owens-Corning Fiberglas Corporation | Clad precious metal bushing and method for making |
| CN1228066A (en) * | 1996-07-12 | 1999-09-08 | 恩吉尔哈德－科拉尔公司 | Bushing base with mounted nozzles |
| CN2421287Y (en) * | 2000-04-17 | 2001-02-28 | 南京玻璃纤维研究设计院 | Platinum alloy bushing for producing basalt fibre |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62207738A (en) * | 1986-03-05 | 1987-09-12 | Nippon Glass Seni Kk | Bushing for producing glass fiber |
| JPH06298543A (en) * | 1993-04-09 | 1994-10-25 | Nippon Glass Fiber Co Ltd | Bushing for producing glass fiber and its production |
| DE10203418C1 (en) * | 2002-01-28 | 2003-02-27 | Heraeus Gmbh W C | Bath used for drawing glass fibers has side walls and a base plate with openings which open into dies on the side of the plate facing away from the inner chamber |
-
2007
- 2007-08-16 CN CN2007800313023A patent/CN101506113B/en active Active
- 2007-08-16 WO PCT/JP2007/065956 patent/WO2008023627A1/en active Application Filing
- 2007-08-21 TW TW96130853A patent/TW200812926A/en unknown
-
2011
- 2011-09-30 JP JP2011217731A patent/JP5403291B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4846865A (en) * | 1988-03-15 | 1989-07-11 | Owens-Corning Fiberglas Corporation | Clad precious metal bushing and method for making |
| CN1228066A (en) * | 1996-07-12 | 1999-09-08 | 恩吉尔哈德－科拉尔公司 | Bushing base with mounted nozzles |
| CN2421287Y (en) * | 2000-04-17 | 2001-02-28 | 南京玻璃纤维研究设计院 | Platinum alloy bushing for producing basalt fibre |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5403291B2 (en) | 2014-01-29 |
| WO2008023627A1 (en) | 2008-02-28 |
| JP2012001434A (en) | 2012-01-05 |
| TW200812926A (en) | 2008-03-16 |
| CN101506113A (en) | 2009-08-12 |
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