CN1026686C - oxynitride glass fibre - Google Patents
oxynitride glass fibre Download PDFInfo
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- CN1026686C CN1026686C CN 91111836 CN91111836A CN1026686C CN 1026686 C CN1026686 C CN 1026686C CN 91111836 CN91111836 CN 91111836 CN 91111836 A CN91111836 A CN 91111836A CN 1026686 C CN1026686 C CN 1026686C
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Abstract
An oxynitride glass which has Si-M1-M2-O-N system and contains SiO2, Si3N4 and M1O in a mole% satisfying the following equations (a) and (b): (SiO2+3Si3N4+M1O)x100 / (100+2Si3N4) = 65 to less than 100 mole% (a) (SiO2+3Si3N4 / M1O = 0.7 to 2.3 (b) wherein M1 is Ca, or Ca and Mg; M2 is a metal except Ca and Mg, a process for preparing thereof and a fiber thereof. The oxynitride glass has excellent hardness and elastic modulus so that it is adapted to a reinforcing material.
Description
The present invention relates to the fiber of a kind of oxynitride glass, its production process and this oxynitride glass.Or rather, the present invention had both related to a kind of oxynitride glass that has high elastic coefficient and good hardness and be suitable for doing strengthening material, related to the fiber of its production process and this oxynitride glass again.
Oxynitride glass of the present invention is made fiber or chip, and it is suitable for doing the starting material of matrix material, as the strongthener of plastics composite and the lining of metal.Block and flaky oxynitrides of the present invention can directly be used to various uses as having high rigidity and high-tensile mold.
Fiber of the present invention is suitable for doing fortifying fibre such as the fibre reinforced plastics (FRP) and the fibre reinforced cement of matrix material.
The structure of oxynitride glass is that oxygen is replaced by III valency nitrogen in oxide glass.It is believed that this replacement is owing to forming closeization that causes this glass reticulattion than the more key of oxide glass.Thereby with general common glassy phase ratio, oxynitride glass has high Young's modulus.
The composition of known oxynitride glass comprises: Ca-Si-Al-O-N, Na-Ca-Si-O-N, La-Si-Al-O-N, Na-B-Si-O-N, Mg-Si-Al-O-N, Si-Al-O-N, Y-Al-Si-O-N, Na-B-Al-P-O-N etc.
These oxynitride glass are by smelting process, solution-gel method, blow N
2Method, the NH of sintered glass
3Methods such as processing are made.
Smelting process is to add in the metal oxide metal nitride and melting at high temperature.The example of such metal oxide has SiO
2, Na
2O, K
2O, La
2O
3, Y
2O
3, ZrO
2, TiO
2, B
2O
3Or the like.The example of such metal nitride comprises Si
3N
4, AlN or the like.
Solution-gel method, have-OH or-the oxide glass presoma and the NH of OR base
3Reaction.The example of such oxide glass presoma has four alkoxyl silicones, four titan-alkoxides or the like.
In the component of known oxynitride glass, the glass of can not obtain to have 15% atomic ratio (being equivalent to 9% weight ratio) or more nitrogen content.That is to say that the known composition of oxynitrides component or chemical combination ratio can not replace oxygen in the oxide glass fully with nitrogen.When the preparation oxynitride glass, escape the oxynitride glass that result's acquisition has low nitrogen content (5-6% weight) in the nitrogenize glass system in the starting material.
Glass fibre is useful as a kind of formed material that strengthens.As a kind of effective ways as the strongthener in plastics or the cement casting, made a kind of matrix material recently, this matrix material is made up of said material and glass fibre.The fiber that generally is used in so conventional matrix material is E glass fibre or S glass fibre, and its intensity is also not enough.That is to say that the maximum elastance of E glass is 7,500kg/mm
2And have the imperial N-672(Imperial N-672 of high elastic coefficient) have only 12,110kg/mm
2
Knownly make the method that the method for oxynitride glass and the block oxynitride glass of making by this method and then melting are made fiber here by solution-gel method, please be ask referring to United States Patent (USP) 4,609,631.The known oxynitride glass fiber that is obtained by solution-gel method only has 8000kg/mm
2Young's modulus, the reinforcing glass fiber of using for matrix material is not enough.On the other hand, the maximum nitrogen content that the known oxynitride glass fiber of being made by the melting again of block oxynitride has is the high elastic coefficient of 15% atomic ratio and 140-180GPa, but such fiber is very expensive, because it contains the valuable yttrium of 42.6-45.6% weight ratio.
The present invention has done that intensive research replaces effectively with nitrogen that oxygen in the oxide glass obtains oxynitride glass and as the fiber of the oxynitride glass with superior strength of strongthener.Therefore, found that oxynitride glass can contain a large amount of nitrogen by increasing the content of CaO, the fiber of being made by smelting process by such oxynitride glass has unusual high strength and high elastic coefficient.
Therefore, providing an oxynitride glass with high rigidity and Young's modulus is purpose of the present invention.
Another object of the present invention provides the method that preparation has the oxynitride glass fiber of high nitrogen-containing and high elastic coefficient.
Further purpose of the present invention provides the glass fibre with high elastic coefficient.
Following description is for those people who is familiar with this technologies, and these and other objects and advantages of the present invention are clearly.
Improved oxynitride glass desired among the present invention has Si-M
1-M
2-O-N system also contains molar percentage and satisfies following equation (a) and SiO (b)
2, Si
3N
4And M
1O:
(SiO
2+ 3Si
3N
4+ M
1O) * 100/(100+2Si
3N
4)=65 are arrived less than 100(mole %) ... (a)
(SiO
2+ 3Si
3N
4)/M
1O=0.7 to 2.3 ... (b)
M in the formula
1Be Ca or Ca and Mg; M
2It is a kind of metal that removes Ca and Mg.
That is to say, by adding a large amount of CaO, or CaO and MgO, resulting oxynitride glass can contain a large amount of nitrogen so that make this glass have unusual high elastic coefficient and hardness.
The method that preparation has the improved oxynitride glass of high elastic coefficient comprises the following step:
(ⅰ) following material is mixed:
SiO
2;
Be selected from and comprise Si
3N
4With a kind of nitride of metal nitride,
Be selected from metal oxide that comprises except that CaO and MgO and a kind of compound of compound that can produce metal oxide by thermolysis;
Be selected from and comprise CaO, CaO+MgO and can produce a kind of compound of compound of CaO or MgO by thermolysis.
Their molar percentage can satisfy following equation (a) and (b):
(SiO
2+ 3Si
3N
4+ CaO+MgO) * 100/(100+2Si
3N
4)=65 are arrived less than 100mole% ... (a)
(SiO
2+ 3Si
3N
4)/CaO+MgO=0.7 to 2.3 ... (b)
CaO in the formula is the molar percentage of CaO or the molecular fraction that can change into the compound of CaO in CaO; MgO is the molar percentage of MgO or the molecular fraction that can change into the compound of MgO in MgO.
(ⅱ) under 1400-1900 ℃ temperature, in inert gas atmosphere, heat this mixture to fusion.
Oxynitride glass fiber of the present invention is made by above-mentioned glass.
Fig. 1 is the diagrammatic cross-section that is used to produce the hot candied equipment of oxynitride glass fiber of the present invention.
Fig. 2. be depicted as the relation of the nitrogen content of the glass that is obtained in Vicks VapoRub (Vickers) hardness and the example, from this relation as can be seen, hardness value increases with the increase of nitrogen content.
Figure 3 shows that the nitrogen content of final glass fibre in the example and the relation of Young's modulus.X-coordinate is represented nitrogen content in the fiber (%) in Fig. 3, and ordinate of orthogonal axes is represented Young's modulus.
Figure 4 shows that one uses the production process of the fishing rod of reinforcing glass fiber.(example 65)
Fig. 5 is the sectional view of the pressure assembly of an optical fiber cable.(example 67).
Fig. 6 is to use the sectional view of the refractory electrical lead of oxynitride glass of the present invention.(example 69).
Figure 7 shows that the time changing curve of the bending strength of the moulded piece that uses the reinforcing glass fiber.(example 70)
Fig. 8 is to use the sectional view of the snubber of oxynitride glass fiber.
Fig. 9 is the perspective view that preparation is used in the device of the oxynitride glass fibre on the flywheel.
Figure 10 a. is the skeleton view of the racket framework of a use oxynitride glass, and Figure 10 (b) is that Figure 10 (c) is the sciagraph that the racket framework of Figure 10 (a) is partly intercepted along the sectional view of Figure 10 (a) A-A ' line intercepting.(example 73)
Figure 11 (a) is to use the protection cloth front view of oxynitride glass fiber, and Figure 111 (b) is the sectional view of Figure 11 (a).(Figure 74)
Figure 12 is to use the skeleton view of the air filtration plate of oxynitride glass fibre.(example (example 75)
Figure 13 is the sectional view of golf club's transmission shaft of a use oxynitride glass fibre.Example 75)
Figure 14 (a) is the sectional view with the pressure cylinder of oxynitride glass fiber, and Figure 14 (b) is the sectional view along the intercepting of Figure 14 (a) A-A line.
Oxynitride glass of the present invention includes 15% or more a large amount of nitrogen, thereby it has take the tight bridge tissue of Ri-N palladium as the basis. Therefore, glass of the present invention has with known glassy phase than glass network structure more closely, and this has caused this glass to have case hardness and high elastic modulus.
The invention provides a kind of is the not low 12500kg/mm of 15-30% and elastic modelling quantity by the cheap raw material of melting and the hot candied nitrogen content that obtains2Glass fibre. According to the present invention Can obtain the high elastic modulus that a kind of known glass fibre can not obtain.
Oxynitride glass of the present invention has Si-M1-M
2-O-N glass system system, wherein in M1Ca or Ca+Mg. Be that this oxynitride glass is Si-Ca-M2-O-N or Si-Ca-Mg-M2-O-N glass system, metal M2Suitable example be Al, Sr, La, Ba, Y, Ti, Zr, Na, K, Sb, B, etc. These metals can be to combine in twos or more. Thereby typical case's composition of this oxynitride glass is: Ca-Si-Al-O-N, Na-Ca-Si-O-N, La-Ca-Si-Al-O-N, Na-B-Ca-Si-O-N, Mg-Ca-Si-Al-O-N, Si-Ca-Al-O-N, Y-Al-Ca-Si-O-N, Na-B-Ca-Si-Al-P-O-N, Ca-Mg-Si-Al-O-N, Sr-Ca-Mg-Si-Al-O-N, Ba-Ca-Mg-Si-Al-O-N, Y-Ca-Mg-Si-Al-O-N etc.
Moreover the oxynitride fiber has so a kind of one-tenth and is grouped into, and the mole percentage of oxide system wherein should satisfy following relation (a) and (b):
（SiO
2+3SiN
4+CaO+MgO）×100/（100+2Si
3N
4)=65 are arrived less than 100mole% ... (a)
（SiO
2+3Si
3N
4)/CaO+MgO=0.7 to 2.3 ... (b)
CaO is the mole percentage of the mole percentage of CaO or the compound that can change into CaO in CaO in the formula; HgO is the mole percentage of MgO or the compound mole percentage that can change into MgO in MgO. Oxynitride glass of the present invention is compared with known oxynitride glass and is contained a large amount of Ca and Mg. As (SiO2+3SiN
4+CaO+MgO）×100/（100+2Si
3N
4) less than the 65(mole) during %, can obtain the glass with crystal structure. As (SiO2+3Si
3N
4) / CaO+MgO is less than 0.7 or greater than 2.3 o'clock, and final glass has less than 15% nitrogen content, and this glass of result does not have high elastic modulus.
In order to obtain oxynitride glass of the present invention, more preferably following material is mixed:
ⅰ，SiO
2;
ⅱ，Si
3N
4Or a kind of other metal nitride.
ⅲ, a kind of metal oxide except CaO and MgO; And
ⅳ, CaO or CaO+MgO.
The suitable example of the metal oxide among the ⅲ is Al2O
3，BaO，Sb
2O
3，SrO，Na
2O，K
2O，La
2O
3，CeO
2，Y
2O
3，ZrO
2，TiO
2Na
2O，K
2O，B
2O
3, etc. Can use the compound that forms above-mentioned metal oxide by thermal decomposition to replace these metal oxides, such as carbonate, hydroxide, oxalates, etc. So the compound of these metal oxides and formation metal oxide combines in twos or more and is used.
Except Si3N
4Outward, the example of the metal nitride that is fit to is AlN, BN etc. Preferably use AlN and Al2O
3, BN and B2O
3 These nitride and Si3N
4Also can be used in combination.
Oxynitride glass with CaO as basis. Oxynitride glass can contain CaO and MgO. Can use the compound replacement CaO and the MgO that form CaO or MgO by thermal decomposition, such as carbonate, hydroxide, oxalates, etc.
These raw material are to satisfy % by mole mutually mixing of following equation (a) and (b):
（SiO
2+3Si
3N
4+CaO+MgO）×100/（100+2Si
3N
4)=65 are arrived less than 100mole% ... (a)
（SiO
2+3Si
3N
4)/CaO+MgO=0.7 to 2.3 ... (b)
CaO is the mole percentage of CaO or the change that can change into CaO in CaO in the formula The mole percentage of compound, MgO are the mole percentages of the mole percentage of MgO or the compound that can change into MgO in MgO.
With these oxides and nitride mixing and heating acquisition oxynitride glass, this mixture of melting is preferably under 1400-1950 ℃ and carries out, and the rate of heat addition is 10-800 ℃/minute, 1 minute to 3 hours time, goes in inert gas or nitrogen atmosphere. This inert gas can be normal pressure. Be melted in the heating furnace, such as electric furnace, image furnace, etc.
Another kind method be in the crucible in air gas neon melting only have hopcalite thing, then grind into powder. Again these oxide powder are mixed with mononitride, at high temperature with inert gas atmosphere in melting, obtain this oxynitride glass.
Then, this oxynitride glass is through cooling off fast or at a slow speed. The oxynitride glass that has cooled off moved be placed on one and be heated in 1100-1600 ℃ the drawing apparatus, in inert gas gas neon, pulled into continuous fiber with the hot candied speed of 20-3000m/min.
Another kind method is to be cooled to 1100-1600 ℃ from melt temperature in the process furnace of drawing apparatus, and with the wire drawing of fusion oxynitride glass, wire drawing is carried out under inert gas atmosphere.
Final glass has optimum N content and the 125%%-25000kg/mm of 15-30af%
2Young's modulus and 70-500kg/mm
2Tensile strength.
When nitrogen content less than 15% the time, this kind glass does not show high Young's modulus.On the other hand, when nitrogen content surpassed 30%, glass is separated out crystal, and this was undesirable.The content of nitrogen is to regulate by the amount of the nitride in raw and auxiliary material.
The diameter of glass fibre is preferably at 3-50 μ m.When diameter during less than this scope, hot candied operation has become difficulty.On the other hand, when diameter surpasses this scope, intensity significantly lowers.
Referring now to the figure that has numerical markings,, the hot candied stove that is used to produce this oxynitride glass fiber illustrates with Fig. 1.The hot candied stove 1 that is used for this glass fibre has borium nitride crucible 2, have a tiny fiber outlet in its bottom and long graphite heater 3 is arranged around the side surface of said crucible 2, stove overcoat 6 is comprising said crucible 2 and well heater 3, also has the nitrogen chamber 5 by glass fibre.
Stove overcoat 6 has thermally-insulated body 10 on its whole inwall, have cooling jacket 11 and 12 on its lower curtate and top and form an inner room that comprises said crucible 2 and hot device 3.The cooling jacket 11 of bottom contacts shape one electrode with said well heater 3.On the other hand, the cooling jacket 12 on top has centre hole; One radiation thermometer 14 is housed, and there is a protectiveness quartz glass plate 13 its underpart.In addition, have a gas inlet 15 on the sidewall of stove overcoat 6, it sends nitrogen into nitrogen chamber 5 is inner rooms that crucible is arranged.In addition, the side also has a fiber outlet 16 under bottom cooling jacket 11, and it can folding, keeps the nitrogen atmosphere with glass contact.
In this specific embodiment, transportable auxiliary chamber 17 is right after in the bottom of said fiber outlet 16, is carrying out wire drawing under the nitrogen atmosphere more completely.Final glass fibre 4 quilts are around to spool 18.
The present invention illustrates by following example, but is not limited to this scope.
The condition and the result of preparation glass sum up at table 1.The nitrogen content of glass fibre is surveyed with Ke Yeda (Kjeldahl) method and the sub-analyser of X-ray photoelectric and is shown in example.
Example 1
SiO
2(22.8mol%), CaO(40.8mol%), MgO(12.0mol%) and Al
2O
3(14.4mol%) be mixed together and under 1500 ℃ of temperature in air atmosphere in fusion 2 hours.Mix and to contain after the thing cooling, in ball mill, be ground into the grain that size is about 10 μ m.Then, with Si
3N
4(10mol%) mix, and be put in the boron nitride crucible 2, be placed in the drawing apparatus shown in Figure 1.Mixture passes through cylindricality carbon heater 3 fusions 30 minutes under 1750 ℃ of temperature, nitrogen neon, and is incubated by outer thermally-insulated body 10.After temperature is reduced to 1500 ℃, with this mixture wire drawing and around to spool 18.Hot candied proceeding under hot candied speed 1000m/min has the continuous fibre that diameter is 20 μ m.The physicals of oxynitride glass fiber is as shown in table 1.
Example 2
Method described in the use-case 1, but change raw-material amount and condition (being shown in table 1), preparation oxynitride glass fiber.
In example 2, oxide compound is mixed and in the fusion 40 minutes in air atmosphere of 1500 ℃ of temperature, this hopcalite again with nitride fusion 20 minutes under 1790 ℃, nitrogen atmosphere.Carry out wire drawing with hot candied speed 1200m/min, obtain having the continuous fibre of diameter 18 μ m and length 3km.The physicals of this oxynitride glass fiber is as shown in table 1.
Example 3
With SiO
2(22.8mol%), Si
3N
4(10.0mmol%), CaO(40.8monl%, MgO(12.0momol%) and Al
2O
3(14.4mol% mixes, and becomes the particle of about 10 μ m sizes in grinding in ball grinder.Then, mixture is put into 2 li of boron nitride crucibles shown in Figure 1, and fusion 30 minutes under 1750 ℃, nitrogen atmosphere.When the temperature of oxynitride is reduced to 1500 ℃ of hot candied temperature, hot candied under hot candied speed 1500m/min, obtain having the fiber of 15 μ m diameters.The physicals of this oxynitride glass as shown in Figure 1.
Example 4
Use-case 3 described the same manners, but raw-material amount and condition (being shown in table 1) changed, prepare this nitrogen oxide glass fiber.In example 4, the mixture of oxide compound and nitride was 1790 ℃ of following fusions of temperature 30 minutes.When temperature is reduced to 1490 ℃ of hot candied temperature,, obtain having the fiber of diameter 15 μ m length 4.5km with hot candied speed 1350m/min wire drawing.
Example 5
Listed oxide raw material and fusion 2 hours under 1500 ℃ of air atmospheres in the mixture table 1.After with this mixture cooling, become size to be about the particle of 10 μ m with the ball mill ball milling.Then with Si
3N
4Mix, put borium nitride crucible into.Mixture fusion in 1750 ℃ of following nitrogen gas neon obtained an oxynitride glass in 30 minutes.
Put this final oxynitride glass into boron nitride crucible 2 (the earthenware tube is to be placed in the drawing apparatus shown in Figure 1).Be heated to 1380 ℃ under the nitrogen atmosphere, wire drawing is on spool.Hot candied speed is 1500m/min, and obtaining diameter is the continuous fibre of 15 μ m.
Example 6
Use-case 5 described same quadrat methods, but raw-material amount and condition (being shown in table 1) changed, preparation oxynitride glass fiber.Carry out wire drawing with hot candied speed 80m/min, obtaining diameter is the continuous fibre of 25 μ m.
Example 7-11,16-18,20,24-34,37-52 and 55
The same manner shown in the use-case 1, but raw-material amount condition (being shown in table 1) changed, preparation oxynitride glass fiber.In these examples, oxide compound fusion 1 hour under 1500 ℃ and air atmosphere.
The physicals of oxynitride glass fiber is also as shown in table 1.As a result, the oxynitride glass fiber that is obtained by routine 7-9 has low nitrogen content and low Young's modulus.
Example 12
With SiO
2(8.6mol%), Si
3N
4(19.4mol%), CaO(59.8mol%, MgO(6.9mol%) and Al
3O
3(5.2mol%) mix and by a roll squeezer at 1500kg/cm
2Down compacting 30 seconds of pressure.Mixture keeps fusion in 3 minutes through being warmed up to 1780 ℃ under nitrogen atmosphere in the image furnace.Then, individual mixture is by a double roll press quick cooling.Final glass is the small pieces with about 25 μ m thickness.
Final glass is put, the crucible 2 in hot candied equipment shown in Figure 1.Under 1570 ℃ of temperature and nitrogen atmosphere, heat, hot candied then, obtain a continuous fibre.
Example 13
With SiO
2(8.6mol%), SiN
3(19.4mol%), CaO(58.3mol%), MgO(6.9mol%), Al
2O
3(5.2mol%) and Y
2O
3(1.5mol%) at 1500kg/cm
2Pressure under compression moulding.This mixture makes its fusion being heated to 1770 ℃ in the image furnace under nitrogen atmosphere.Mixture is dripped on the iron plate below the stove, obtain oxynitride glass.
Then, use-case 12 described with quadrat method with the hot candied fiber that obtains of final glass.
Example 14 and 54
With 13 described same quadrat methods, but change raw-material amount and condition (being shown in table 1), make the oxynitride glass fiber.
Example 15,19 and 21
Use-case 5 described same quadrat methods, but change raw-material amount and condition (being shown in table 1), preparation oxynitride glass fiber.
Example 22,35 and 36
With with example 3 described same quadrat methods, but change raw-material amount and the described condition of table 1, preparation oxynitride glass fibre.
Example 23
The starting material that table 1 is listed (oxide compound and nitride) mix, and grind to form the particle that size is about 10 μ m with ball.Mixture is put into boron nitride crucible fusion under nitrogen atmosphere, 1730 ℃ of temperature, obtains an oxynitride glass.
The oxynitride glass of gained is put in the boron nitride crucible 2 in the drawing apparatus shown in Figure 1, under nitrogen atmosphere, be heated and 1530 ℃ hot candied down, obtain a continuous fibre.
Example 53
With with example 12 described same modes, but change raw-material amount and condition (being shown in table 1), preparation oxynitride glass fibre.
Example 56-61
With with example 7 described same modes, processing list 1 described oxide compound and nitride, but can not obtain oxynitride glass.
In example 56 and 57, (SiO
2+ 3Si
3N
4+ M
1O) * 100/(100+2SiO
2) being less than 65mol%, acquisition can have the imperfect glass of part crystal phase.
In example 58 and 59, (SiO
2+ 3Si
3N
4)/M
1O is less than 0.7, the fusion fully of this mixture, and what obtain is crystal.
In example 60 and 61, (SiO
2+ 3Si
3N
4)/M
1O is greater than 2.3, and mixture can be melted, and obtains a crystal phase.
Example 62-64
With example 7 described same methods, but change raw-material amount and condition (being shown in table 1), preparation oxynitride glass fiber.
The physicals of oxynitride glass fiber is also as shown in table 1.As a result, oxynitride glass has low Vickers' hardness and Young's modulus.
The physicals of these oxynitride glasses under tabulate shown in 1.
(table 1)
(application)
The application of oxynitride of the present invention is more properly illustrated by following example.
Example 65(fishing rod)
Fishing rod with oxynitride glass fiber manufacturing of the present invention.Figure 4 shows that the production process of fishing rod.(size: 20-100cm * 200-5000cm, the fineness of glass fibre is 15 μ m, fibre count: 670g/km), immerse a unsaturated polyester resin and obtain prepreg 21 in the fabric of the oxynitride glass that obtains in above-mentioned example 5.Prepreg 21 is wrapped in metal-cored 22(size: diameter 3-12mm * length 300cm), fix with plastic adhesive tape.Add thermomaturation then.The fishing rod that obtains at last has the intensity same Young's modulus more higher than common product.
Example 66(is used for the insulating material of commissural organ)
A kind of insulating material that is used for commissural organ of powder production from oxynitrides acquisition of the present invention.With the oxynitride glass fibrous bundle (fiber diameter: that obtains in the example 55 μ m) in a ball mill (the vibration nitrogen ball mill of band aluminium silicon (almina) ball, 1200rpm) middle broken 10 minutes.Final efflorescence fiber and poly-terephthalic acid butanediol ester toner done mix, after this, stir an extrusion machine by single shaft and stir.By injector the gained mixture is formed the insulating material rectangle testpieces (1.5 * 8cm) that a commissural organ uses.Testpieces is without any distortion.The temperature of the thermal distortion of test specimen is 225 ℃.
The fibre-optic tension member of example 67.()
With Pul trusion method oxynitride glass macrofiber in the example 5 and Resins, epoxy (as matrix) are made fibre-optic tension member.
Fig. 5 is the pressure assembly sectional view of optical fiber cable.Fibrous structures 26 has the tension member 27 of oxynitride glass, removes in addition, and be many photoconductive fiber leads 28 of coaxial placement, in the middle of tension member 27 and lead 28, and lead into 28 li with elastomerics 29 fillings, around elastomerics 29 tail dragon layer 30.
Example 68(shielding case film)
(size is 500 * 1000cm, and glass fiber diameter is 13 μ m, fibre count 500g/km) dipping unsaturated polyester resin (200g) obtains a sheeting (fibre-bearing: 55wt%) in the fabric of the oxynitride glass that obtains in above-mentioned example 5.The film that is used for shielding case that makes has good characteristic as follows: tensile strength: be not less than the 85kg/cm width, unit elongation: be no more than 3.5%, radio wave propagation coefficient: be not less than 96%.
Example 69(flame proof electrical lead)
Fig. 6 is to use the flame proof electrical lead of oxynitride glass system of the present invention.Single core copper conducting band 33(3 * 8mm in lead 31
2) around, be surrounded by the flame retardant coating 34(coating width 20-100cm that oxynitride glass cloth is made, coated length 2000-5000cm, the diameter of fiber: 10-15 μ m).The chromatograph 36 that vinyl chloride resin is arranged on flame retardant coating 34.The resistivity against fire of final lead is tested by Japanese fire prevention council's standard (No.7, date 1978,10,16), succeeds.
The glass fiber-reinforced cement pressing mold of example 70()
In the composition of sand-cement slurry, add a whipping agent (0.2wt%) and obtain the foaming mortar.In the foaming mortar, add the 10(volume then) oxynitride glass that obtains by above-mentioned example 5 of %, obtain a foaming premix after the mixing.With the premix drying, regulate water-content to 15%.The final material that forms cuts into a cubes (30cm) and obtains a test block by suppressing (150kg) moulding, and it was by ageing and maintenance 15 days.Fig. 7 has represented that the time of the bending strength of final moulded piece changes (mark 0)
Outside the alkali-resistivity oxide glass of making fortifying fibre (MINERON-M #801, the diameter of fiber: 20 μ m, staple length: 25mm, bundle fiber is several 160, is made by Asahi fiberglass company), obtain a test block with above-mentioned the same manner.The result also illustrates (mark) at Fig. 7.
Example 71(snubber)
Fig. 8 is the sectional view of a snubber, and this snubber is to make by the prepreg in the slaking mould.This prepreg is by the glass fibre in the artificial resin dipping example 5 is obtained.In Fig. 8, bearing 41 is by making by this glass fiber-reinforced a kind of artificial resin, its cross section shape such as U word, and as shown in Figure 8, bearing 41 has boss on the free-ended main part of the force of the upper limb 43 of its U-shaped and lower rim 44.Moreover these positions of bearing immense strength can strengthen by adhering to or embedding reinforcing member.For example, part or all parts 45 that is embedded into can be embedded in main part of the force.The front surface 46 of bearing 41 can be enhanced, thereby forms groove 47.Prevent that with fin 48 upper limb 43 lower rims 44 are subjected to bending force.Fin is the inboard at bearing 41.Such fin 48 has satisfied the function of connect elements 49, and the 49th, connect to holistic with bearing 41.
Example 72(flywheel)
With SiO
2(22.8mol%), CaO(40.8mol90), MgO(12.0mol%) and Al
2O
3(14.4mol%) mix, under 1500 ℃ of temperature and in the air atmosphere, burnt 2 hours.Afterwards, mixture is fractured into powder (size 1-10 μ m), puts feeder shown in Figure 9 51 into.Si in powder in the feeder 51 and the feeder 52
3N
4Powder mixes in continuous mixing device 53, Si
3N
4Inlet amount be linear increasing, be sent to hot candied stove 54 then in order that the content of nitrogen is changed to 12wt% from 1wt%.Powder raw material fusion in hot candied stove, and, remain on 1380 ℃ from the wire drawing of crucible bottom.Handle with roll squeezer 56 on the surface of fiber.Then, accumulate one by manifold 57 and on spool 558.
Then, fiber strand is unclamped in one direction, form prepreg with resin impregnation.Nitrogen content in this prepreg increases continuously to other direction from a direction.This prepreg from the low end of nitrogen content around a last axle.Therefore obtain a flywheel that increases continuously to edge mould modulus from the center.
Example 73(racket framework)
Figure 10 (a) is to use the perspective diagram of the games racket frame of the oxynitride glass fiber that is obtained by example 5.Shown in Figure 10 (a), framework 61 integral body are by the ellipse batting part 62 that has silk string, and the handle 64 of racket, neck 63 connect said batting part 62 and racket handle 64.Figure 10 (b) is the sectional view of getting along A-A ' line of Figure 10 (a).Batting part 62 has a box type profile structure, and this structure is that core and the fibre reinforced plastics shell 66 around it that resin 65 constitutes formed by the foaming people.Fibre reinforced plastics shell 66 shown in Figure 10 (c) by the oxynitride glass fiber help or rib cloth 67 and oxynitride glass fiber or carbon fiber 68 are formed.That is to say that oxynitride glass fiber 67 arranges that along the edge directions X of racket framework other oxynitride glass fiber or carbon fiber 68 are along arranging with the rectangular direction of the direction of said oxynitride glass fiber 67 (Y and Z direction).
Though, oxynitride glass fiber or carbon fiber preferably along and the width of framework or batting width parallel layout the fully, these fibers can ± 45 ° maximum deviation arranges, preferably is no more than ± 30 °.
Example 74(protection cloth)
Figure 11 (a) and Figure 11 (b) are to use the front view and the sectional view of the oxynitride glass fiber protection cloth in the example 5 respectively.As shown in Figure 11, protection cloth is made up of oxynitride glass layer of fibers 72 and tectum 73, and it is sewed up or engage by an adhesive agent.Glass layer 72 preferably is made up of multilayer oxynitride glass fabric, and preferably 3, because it has superior heat impedance and Young's modulus.Tectum 73 can be general coating.Tectal surface can also further use synthetic resins coated with obtaining water-repellancy.
Example 75(air is crossed the ripple plate)
Figure 12 is the perspective diagram of the air filter made of the oxynitride glass in the use-case 5.Oxynitride glass fiber 74 is made into thin slice and overlays on (METSUKE:80g/m on the non-woven fabric 75 of polypropylene fibre
2, thickness: 0.5mm) obtain a dustproof glass layer of fibers (METSUKE:10g/mm
2, thickness 0.05mm).The final strainer pressure-losses is low, intensity is high, the dust suction coefficient good.
The bat of example 76(golf club)
Figure 13 is the cross-sectional view of golf club's bat of making of the oxynitride glass fiber in the use-case 5.
As Figure 13, the carbon fiber (Torayca of epoxy resin-impregnated; T200, Toray company limited makes) use filament winding method around a conical metal-cored (end diameter: 4mm of going up; Outside diameter 14mm; Length 1300mm) forms internal layer 77 with thickness 3mm.This prepreg is that the oxynitride glass fiber that will make in the epoxy resin impregnated example 5 obtains, and it is formed the skin 76 of 1mm thickness on internal layer 77.On outer 76, fix a film with high release property, solidify and the demoulding after, final product is cut, and skin is ground to desired size and hardness, obtains the fibre-reinforced plastics bat of a golf club.
Example 77(pressure cylinder)
Figure 14 (a) is to use the sectional view of the oil pressure cylinder of the oxynitride glass fiber in the example 5.Figure 14 (b) is the sectional view along the intercepting of A-A line.In Figure 14 (a), pressurized vessel 78 is made up of inner casing 80, the shell 90 of plastics and the lining 79 that forms the outlet of pressurized vessel 78.
Shown in Figure 14 (b), inner casing 80 is by being formed by 81 enhanced resin layers 82 of fiber.The suitable example of this fiber is glass fibre (as the oxynitride glass fiber, E-glass fibre, S-glass fibre); Steel fiber (as steel fiber); Inorganic fibre (as carbon fiber, boron fibre, SiO fiber, aluminium silicon (almina fiber; Organic polymer fiber (as the aramid fiber, trevira, nylon fiber and its mixing.Consider its relative intensity, what preferentially select is the oxynitride glass fiber.Fiber in the resin layer 82 can form the fabric shown in Figure 14 (b), in one direction the low plate that constitutes by fibrous thin slice, by regenerated fiber or any general type of fiber.The diameter of fiberoptic fiber, the thin slice or the thickness of fabric can be any suitable scopes.Preferably with 40% to 80% the reinforcing fiber that accounts for the resin layer matrix.
The shell 90 that overlays on said internal layer cylinder 80 for reinforcing is made up of the protection resin layer 92 of fortifying fibre layer 91 and protective layer 91.Fortifying fibre layer 91 will contain the oxynitride glass fiber at least.Preferably on resin layer 82, wind with the oxynitride glass fibrous rib.Layer of fibers 91 can further contain any other fortifying fibre.The resin of the preferential protective layer of selecting 92 can be general resin as thermosetting resin, thermoplastic resin or other.
In addition, pressure cylinder can be provided with fortifying fibre by containing to form as the single-layer resin matrix of the oxynitride glass fiber of strongthener in shell.As strongthener, can have with oxynitride glass fiber and appropriate form above-mentioned inorganic, organic or steel fiber.
Claims (3)
1, a kind of oxynitride glass fiber is characterized by and has Si-M
1-M
2-O-N system and the SiO that contains
2, Si
3N
4And M
1Omole% satisfies following equation (a) and (b):
(SiO
2+ 3Si
3N
4+ M
1O) * 100/ (100+2Si
3N
4)=65 are arrived less than 100mole% ... (a)
(SiO
2+ 3Si
3N
4)/M
1O=0.7 to 2.3 ... (b)
M in the formula
1Be Ca, or Ca and Mg; M
2It is a kind of metal except that Ca and Mg;
The diameter of described oxynitride glass fiber is 3-50 μ m;
The Young's modulus of described oxynitride glass fiber is not less than 12500kg/mm
2
The nitrogen content of described oxynitride glass fiber is 15-30%.
2, oxynitride glass fiber according to claim 1 is characterized by described M
1Be Ca.
3, oxynitride glass fiber according to claim 1 is characterized by described M
1Be Ca and Mg.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP132861/87 | 1987-05-28 | ||
| JP132860/87 | 1987-05-28 | ||
| JP13286087 | 1987-05-28 | ||
| JP223391/87 | 1987-09-07 | ||
| JP22339187 | 1987-09-07 | ||
| CN 88103119 CN1016775B (en) | 1987-05-28 | 1988-05-27 | Oxynitride glass and its preparation |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88103119 Division CN1016775B (en) | 1987-05-28 | 1988-05-27 | Oxynitride glass and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1064854A CN1064854A (en) | 1992-09-30 |
| CN1026686C true CN1026686C (en) | 1994-11-23 |
Family
ID=27178903
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91111836 Expired - Fee Related CN1026686C (en) | 1987-05-28 | 1988-05-27 | oxynitride glass fibre |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1026686C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109231818A (en) * | 2018-10-10 | 2019-01-18 | 内蒙古科技大学 | The production method of oxynitride glass and oxynitride glass |
-
1988
- 1988-05-27 CN CN 91111836 patent/CN1026686C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1064854A (en) | 1992-09-30 |
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