CN103370288B - The method of joining of aluminum oxide conjugant and alumina sintered body - Google Patents
The method of joining of aluminum oxide conjugant and alumina sintered body Download PDFInfo
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- CN103370288B CN103370288B CN201280008843.5A CN201280008843A CN103370288B CN 103370288 B CN103370288 B CN 103370288B CN 201280008843 A CN201280008843 A CN 201280008843A CN 103370288 B CN103370288 B CN 103370288B
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- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
- B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
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Abstract
The present invention relates to a kind of aluminum oxide conjugant alumina sintered body being engaged with each other by junction surface.The aluminum oxide that described junction surface is more than 30 μm by thickness is formed, and by the aperture length on the thickness direction at described junction surface be 40 ~ 100% of the thickness at described junction surface thick independent pore, be do not sinter region and the relative density of the fine pores of less than 5 μm containing aperture be that the sintering region of the densification of more than 98% is formed.
Description
Technical field
The present invention relates to the method for joining of aluminum oxide conjugant that alumina sintered body is engaged with each other and alumina sintered body, more specifically, relate to the large component that is applicable to length extending to several meters and meet the aluminum oxide conjugant of high purity and the such requirement of high strength, and for the method for joining of the alumina sintered body that makes such aluminum oxide conjugant.
Background technology
In recent years, be intended for the quality in the various manufacture field of raising and productivity, for the ceramic parts of engine used in production purposes, require to maximize and high purity.Particularly for making the large component extending to several meters, traditional one-piece type ceramics forming firing technology is difficult to reply.So, being necessary to develop such technology: make multiple little ceramic sintered bodies (block material) and combine, by only carrying out local heating to engage to their joint part, thus making required parts.In addition, requiring in the semiconductor-fabricating device of thermotolerance and erosion resistance and chemical plant etc., impurity element is strict restriction to being mixed into of goods, has high purity for used part requirement.Particularly, in the large size ceramic pipe (duct member) used at the component parts (it is for the manufacture of lithium ion secondary battery anode material) as rotary kiln, need such massive article: it has high purity and high hot strength, largest diameter reaches about 30cm, and length is maximum reaches about 5m.
In the method for joining of general ceramic sintered bodies, having oxide solder method and refractory metal method etc., owing to there is the deterioration with hot strength that is mixed into of impurity element in these method of joining, is therefore not preferred for such use.In addition, such as solid phase pressurization bonding method, hanker making engaged material load high pressure adding, this is difficult in the manufacture of large component, can not meet the requirement of this large component making.
Comparatively speaking, as not pressurizeing, ceramic sintered bodies is engaged with each other and gained conjugant can maintain highly purified method of joining, known such technology: use by being scattered in the slurry formed in pure water carrying out bonding by forming identical ceramic particle with this ceramic sintered bodies, and carry out burning till and engage (with reference to patent documentation 1).
But, in the method for joining described in above-mentioned patent documentation 1, except bond strength is less than except the 100MPa thus insufficient such problem of bond strength, the thickness also also existed due to knitting layer be 0.5 μm thus very thin thus the such problem of the joint of large component cannot be applicable to.Its reason is, for the joined face in order to make the ceramic sintered bodies (block material) that large component uses in the bonding, such as, when tubular body, because diameter is greatly to number more than 10cm, so be usually difficult to make the Flatness of end face reach less than 1 μm, in order to be considered in the method for joining described in above-mentioned patent documentation 1 need the Flatness of maximum about 0.1 μm to complete joined face, be to spend significant cost thus unpractical.Consider from the angle of cost, by carrying out grinding processing to the end face of large ceramic sintered bodies, to realize high precision be preferred like this, though therefore desirably joined face concavo-convex for several 10 μm also can by the method for joining of allowing.
As other method of joining, known following technology: in the joint of beta-oxidation aluminum pipe and vitrified pipe, alumina slurry is applied in joined face as intercalated material with the thickness of about 0.2mm, two pipes are connected together and after drying, are obtained grafting material (with reference to patent documentation 2) by microwave heating.
But the method for joining described in above-mentioned patent documentation 2 is the special methods that limitation is applied to the large βAl2O3 of microwave absorbing.What be typically used as structural ceramics is α-aluminum oxide, and its microwave absorbing is very little, is therefore usually difficult to be heated by microwave.If wish with microwave heating, then need to add the impurity that can absorb microwave well, but in this case, aluminum oxide attachment are not just highly purified.In addition, when using microwave heating, owing to not using thermopair, be difficult to carry out temperature measuring, thus correctly can not control the temperature of engaged material, therefore there is the danger of the engaged material damage caused due to the heating of burst and the problem of the heating with reproducibility and so on cannot be carried out.In addition, in above-mentioned patent documentation 2, the record of bond strength is not had, if consider the problems referred to above, can stably obtain bond strength be also a query, even if obtain conjugant, its intensity is also probably several below 10MPa, easily infers that the deviation its measured value is large.
In addition, describe in the method for joining described in above-mentioned patent documentation 2: in order to homogeneous heating, rotate with per minute 10 turns in microwave sintering device under the state that engaged material supports weight, but large size ceramic sintered compact is rotated in the same terms in microwave sintering device is technically difficult.Due to these problem points, using the method as needing the method for joining of highly purified large-scale alumina sintered body to be unpractical.
Therefore, present situation is the high strength method of joining not having to maintain highly purified compactness alumina sintered body, therefore as rotary kiln large size ceramic pipe, only commercially available have the such commodity of Large Tube below: described Large Tube is the pipe formed by the porous ceramics integrally burnt till by large-scale molding or the pipe be made up of compactness sintered compact docking, be accommodated in and have in the framework of special tectonic, and apply stress under compression from two ends, carry out being mechanically connected thus obtaining.But in the former case, voidage is maximum up to about 25%, flexural strength is maximum also only has about 8MPa, therefore also exists and cannot tolerate heavily stressed such problem.In addition, in the latter case, have that the junction surface section of having is poor, device is complicated and huge and so on problem.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2010-18448 publication
Patent documentation 2: Japanese Unexamined Patent Publication 8-59358 publication
Summary of the invention
Carrying out the present invention to solve the problems of the technologies described above, the object of the present invention is to provide a kind of owing to there is high bond strength and excellent erosion resistance, can be formed in the mode that junction surface is free from foreign meter, for the Flatness of the joined face of engaged material, there is the aluminum oxide conjugant that thus high permission can be applicable to large component well simultaneously; Be made up of this aluminum oxide conjugant and be suitable for being used as the duct member of the rotary kiln component parts that uses in the manufacture of lithium ion secondary battery anode material etc.; And can by heat-treating the method for joining of the alumina sintered body making this aluminum oxide conjugant at low load.
To achieve these goals, according to the present invention, provide the method for joining of following aluminum oxide conjugant, duct member and alumina sintered body.
[1] a kind of aluminum oxide conjugant, it is aluminum oxide conjugant alumina sintered body being engaged with each other by junction surface, the aluminum oxide that described junction surface is more than 30 μm by thickness is formed, and by the aperture length on the thickness direction at described junction surface be 40 ~ 100% of the thickness at described junction surface thick independent pore, be do not sinter region and the relative density of the fine pores of less than 5 μm containing aperture be that the sintering region of the densification of more than 98% is formed.
[2] the aluminum oxide conjugant Gen Ju [1], use the test film cut from described aluminum oxide conjugant in the mode containing described junction surface, the flexural strength at room temperature measured for benchmark with JIS R1601 is for more than 200MPa, and the flexural strength in 1200 DEG C of air measured for benchmark with JIS R1604 is for more than 100MPa.
[3] duct member, it is the duct member be made up of the aluminum oxide conjugant described in [1] or [2], and the compactness alumina sintered body that to have by described junction surface be more than 95% by relative density is engaged with each other the connected structure obtained.
[4] duct member Gen Ju [3], it is used as the component parts of the rotary kiln used in the manufacture of lithium ion secondary battery anode material.
[5] a kind of method of joining of alumina sintered body, it is the method for joining of the alumina sintered body that alumina sintered body is engaged with each other, wherein, to be added with the pure water of dispersion agent as dispersion medium, be prepared in this dispersion medium and be only added with the alumina slurry that obtains as solids component of alumina particle that purity is more than 99.8%, after in the joined face this alumina slurry being applied to described alumina sintered body, joined face is docked each other, the thickness at the junction surface be made up of described alumina slurry between joined face is adjusted to more than 30 μm, directly carry out drying, make interim conjugant, with the face of described joined face pressure for the mode of more than 0.015MPa is to this interim conjugant applying load, in this case, more than 1300 DEG C at the temperature of less than 1700 DEG C, heat-treat in air, sinter described junction surface thus, thus described alumina sintered body is engaged with each other.
The method of joining of the alumina sintered body [6] Gen Ju [5], the content of the alumina particle in described alumina slurry is greater than 65 quality % and is less than 77.5 quality %.
About aluminum oxide conjugant of the present invention, as as described in the method for joining of alumina sintered body of the present invention described later, due to junction surface can be formed when not carrying out use microwave heating by carrying out sintering in an atmosphere, so there is no necessary interpolation in junction surface can the impurity of good absorption microwave, be not only the alumina sintered body as engaged material, and by they articulate junction surfaces, can only be made up of highly purified aluminum oxide.So aluminum oxide conjugant of the present invention does not exist the deterioration of erosion resistance or the intensity caused by impurity residual in junction surface, high bond strength and excellent erosion resistance are given play to, the danger be not simultaneously easily polluted by the external foreign matters.Therefore, aluminum oxide conjugant of the present invention can be widely used in various large-sized structural component, particularly can be suitable as the large component used in the production purposes of semiconductor-fabricating device and chemical plant parts etc. (they all require to be made up of the high purity material of the danger not being mixed into impurity element).In addition, thickness due to the junction surface of aluminum oxide conjugant of the present invention is more than 30 μm, even if therefore the Flatness of engaged material end face (joined face) is several 10 μm, also can absorb that this is concavo-convex, the accurately machined requirement for joined face can be reduced thus.That is, do not need to carry out high-precision processing to large-scale engaged material, even therefore large-scale conjugant, can make with low cost yet.In addition, as mentioned above, there is the concavo-convex of the absorption junction surface, junction surface of well-to-do thickness, make the full engagement of joined face become possibility thus, played high bond strength.And as mentioned above, junction surface is only formed by highly purified aluminum oxide, can be made it not containing impurity such as glass, therefore, even if high bond strength also can be maintained in the hot environment of 1200 DEG C, thus also go for the purposes needing thermotolerance.
The duct member that aluminum oxide conjugant of the present invention is applied to one of its representative purposes obtains by duct member of the present invention.Because this duct member has given play to the effect of aluminum oxide conjugant of the present invention as above, therefore, it is possible to be suitably used as particularly to need the large-scale component parts of high purity, high strength (component parts of the rotary kiln such as, used in the manufacture of lithium ion secondary battery anode material).
According to the method for joining of alumina sintered body of the present invention, the aluminum oxide conjugant of the present invention with excellent effect as above can be made.In addition, about the method for joining of alumina sintered body of the present invention, due to can by an atmosphere, at low load the alumina sintered body as engaged material is heat-treated and engages, even therefore when making large-scale conjugant, also can not use large-scale hot pressing furnace etc. and being engaged by common air furnace.
Brief Description Of Drawings
Fig. 1 is the schematic diagram that an example of aluminum oxide conjugant of the present invention and the schematic configuration as the interim conjugant of its precursor are shown.
Fig. 2 is the SEM photo in the cross section, junction surface of aluminum oxide conjugant of the present invention.
Fig. 3 is the optical microscope photograph at the junction surface of the aluminum oxide conjugant of comparative example 2.
Embodiment
Based on specific embodiments, the present invention will be described below, but the present invention is not construed as limited to these embodiments, without departing from the present invention, based on the knowledge of those skilled in the art, various change, amendment and improvement can be carried out.
Aluminum oxide conjugant of the present invention is that alumina sintered body is engaged with each other by junction surface and forms, be primarily characterized in that, the aluminum oxide that described junction surface is more than 30 μm by thickness is formed, and by the aperture length on the thickness direction at described junction surface be 40 ~ 100% of the thickness at described junction surface thick independent pore, be do not sinter region and the relative density of the fine pores of less than 5 μm containing aperture be that the sintering region of the densification of more than 98% is formed.
Fig. 1 is the schematic diagram that an example of ceramic joined article of the present invention and the schematic configuration as the interim conjugant of its precursor are shown.The ceramic joined article of the present invention with feature described above can be made by the method for joining of alumina sintered body of the present invention.
In the method for joining of alumina sintered body of the present invention, first, to be added with the pure water of micro-dispersion agent as dispersion medium, only add in this dispersion medium purity be the alumina particle of more than 99.8% as solids component, mix and blend is to prepare alumina slurry.Herein, if interpolation sintering aids etc. are as solids component, then meeting residual impurity in junction surface, thus cause the pollution etc. that the deterioration of erosion resistance, the deterioration of hot strength, impurity element cause, be not preferred.As dispersion agent, such as, poly carboxylic acid ammonium salt etc. can be used.It should be noted that, when not adding dispersion agent in pure water, be difficult to add alumina particle in a larger amount with high density under the state with mobility, thus be difficult to obtain the junction surface with high bond strength.
Preferably make the content of the alumina particle in alumina slurry for being greater than 65 quality % and being less than 77.5 quality %.If the alumina content in alumina slurry is below 65 quality %, then forms large cavity at junction surface due to moisture evaporation during alumina slurry drying, cause intensity to reduce sometimes.On the other hand, when the alumina content in alumina slurry is more than 80 quality %, the mobility of alumina slurry is deteriorated, cannot in whole joined face coating sizing-agent equably, produce sometimes engage uneven.In addition, although can coating sizing-agent equably when 77.5 quality %, as shown in the optical microscope photograph of Fig. 3, between junction surface and joined face, generate crackle 30, cause intensity to reduce sometimes, therefore not preferred.The Forming Mechanism of this crackle 30 does not still understand, it is believed that one of reason is: be coated with disposed slurry surface drying and form film, which hinders the adhesion of joined face and slurry.
Next, the alumina slurry prepared is applied in the joined face of both alumina sintered body 1a and 1b or the joined face of wherein one, the joined face of alumina sintered body 1a and 1b is docked each other, and the thickness at the junction surface (junction surface before sintering) 2 be made up of described alumina slurry between this joined face is adjusted to more than 30 μm, directly carry out drying, make interim conjugant 1A.When the thickness at this junction surface is less than 30 μm, exists and cannot absorb the concavo-convex of joined face thus the danger that is not engaged with each other of alumina sintered body 1a and 1b.It should be noted that, although for the upper limit of the thickness at junction surface, there is no particular limitation, if but the thickness at junction surface is blocked up, according to circumstances, the size that there is the thick independent pore formed in junction surface becomes excessive and makes the possibility that bond strength becomes insufficient, and therefore the thickness at junction surface is preferably less than 100 μm.
Then, in an atmosphere the interim conjugant 1A made is heat-treated.Sintered the junction surface 2 of interim conjugant 1A by this thermal treatment, obtain the aluminum oxide conjugant 1B of the present invention that the junction surface 3 after by sintering makes alumina sintered body 1a and 1b be bonded together.This thermal treatment is carried out under following state: be more than 0.015MPa with the face of joined face pressure, be preferably the mode applying load of 0.015 ~ 0.030MPa.When the face of joined face during thermal treatment is pressed less than 0.015MPa, between junction surface and joined face, create the crackle extending to several 100 μm, bond strength deterioration.The face pressure energy of joined face regulates enough in the following manner: such as, as shown in Figure 1 in the mode making alumina sintered body 1a and 1b be above-below direction to arrange interim conjugant 1A, the weight of predetermined quality is placed in the top of interim conjugant 1A.As weight, such as, can use alumina sintered body aptly.It should be noted that, when alumina sintered body 1a only produces the face pressure of more than 0.015MPa in joined face due to himself weight, what there is no need load weight and so on comes from outside loading.Such as, by length be the square of the alumina sintered body of about 1m or cylinder vertical stack to engage time, the face pressure of the joined face produced by the own wt of alumina sintered body is about 0.04MPa, in the joint of this large scale sintering body, the conjugant with abundant intensity can be obtained when load does not come from outside loading.It should be noted that, the thermal treatment under the low loading of this degree can use common air furnace to carry out.
Described thermal treatment is carried out at the temperature of less than 1700 DEG C more than 1300 DEG C.When thermal treatment temp is less than 1300 DEG C, the alumina powder jointed sintering at junction surface does not fully carry out, and cannot obtain sufficient bond strength in junction surface.On the other hand, if more than 1700 DEG C, then there is the particle growth of sintered compact and make the mechanical properties of mother metal that the danger of deterioration occur.
If with above-mentioned such set joined face face pressure and thermal treatment temp heat-treat, then for interim conjugant 1A by the alumina powder jointed junction surface 2 formed, there is the contraction of volume along with alumina powder jointed sintering in one subregion, thus carried out densification, but do not shrink due to alumina sintered body 1a and 1b as to-be-connected body, therefore densification is not carried out in other region, thus formation does not sinter region, residual a lot of fine pores.In addition, by the contraction in the region through densification as above, in other region, junction surface is stretched in the horizontal direction, thus in junction surface, form thick independent pore.So as this heat treated result, conjugant 1A by the alumina powder jointed junction surface 2 formed become by the aperture length on the thickness direction of junction surface be 40 ~ 100% of junction surface thickness thick independent pore 20c, be do not sinter region 20a and the relative density of the fine pores of less than 5 μm containing aperture be the junction surface 3 that the sintering region 20b of the densification of more than 98% is formed, using this junction surface 3 be combined as alumina sintered body 1a and 1b of engaged material, thus obtain aluminum oxide conjugant 1B of the present invention.
Fig. 2 is the SEM photo in the cross section, junction surface of aluminum oxide conjugant of the present invention.Can be confirmed by this photo: junction surface 3 be by (1) aperture be the fine pores of less than 5 μm intensive do not sinter region 20a, thick independent pore 20c that sintering region 20b that (2) relative density is the densification of more than 98% and (3) aperture length on the thickness direction at junction surface 3 are 40 ~ 100% of the thickness at junction surface 3 formed.In addition, do not sintering in region 20a and sintering region 20b, junction surface 3 is touched with upper and lower alumina sintered body (engaged material), does not observe crackle etc., know that junction surface 3 carries the combination of alumina sintered body thus in joint interface.
It should be noted that, by there is several thick independent pore 20c in junction surface 3, a part for joined face is made to have the non-engaging zones do not combined, but these thick independent pore 20c are not interconnected, but isolated existence, therefore be unlikely to form large crackle, the deterioration of the bond strength caused by the existence of thick independent pore 20c is also not serious.In addition, when thermal treatment, by allowing that junction surface is shunk to horizontal direction (direction vertical with the thickness direction at junction surface), there is no need to shrink in a large number to vertical direction (thickness direction at junction surface), therefore sintering region 20b and do not sintering in the 20a of region, further suppress the generation of the sharp crack of inside, crosscut junction surface 3 in the horizontal direction, greatly can not damage bond strength.
As a result, aluminum oxide conjugant of the present invention shows high intensity.Specifically, use the test film cut from aluminum oxide conjugant of the present invention in the mode containing junction surface, as the flexural strength under the room temperature measured for benchmark with JIS R1601, the intensity of more than 200MPa can be shown.In addition, as the flexural strength in 1200 DEG C of air measured for benchmark with JIS R1604, the intensity of more than 100MPa can be shown.
Duct member of the present invention is the duct member be made up of aluminum oxide conjugant of the present invention, the connected structure that the compactness alumina sintered body that to have by described junction surface be more than 95% by relative density is engaged with each other.The duct member that aluminum oxide conjugant of the present invention is applied to one of its representative purposes obtains by this duct member.About this duct member, as alumina sintered body (namely, engaged material), employing relative density is more than 95% such compactness material, in addition, because this duct member has given play to the effect of aluminum oxide conjugant of the present invention as above, therefore, it is possible to be suitably used as particularly to need the large-scale component parts of high purity, high strength (component parts of the rotary kiln such as, used in the manufacture of lithium ion secondary battery anode material).
Embodiment
Based on embodiment, the present invention will be described in more detail below, but the present invention is not limited to these embodiments.
(research of the alumina content in alumina slurry)
Be more than 99.5% by aluminum oxide purity, relative density be more than 99.0% commercial alumina sintered compact be processed into 20mm × 16mm × 5mm, prepare several with wheel grinding 20mm × 16mm face of No. #200 and the test film obtained.Using the mass ratio of 17:1 add in pure water as dispersion agent with ammonium polyacrylate salt be main component Zhong jing grease company make セ Le Na D305(trade(brand)name), fully stir, prepare dispersion medium.Relative to this dispersion medium, interpolation purity is more than 99.8%, median size is the alumina particle of 600nm, make that its content is as shown in table 1 is respectively 65.0 quality %, 69.5 quality %, 74.5 quality %, 77.5 quality %, 80.0 quality %, and stir, obtain the slurry that dispersing and mixing in dispersion medium has alumina particle.In addition, the vacuum outgas that vacuum pump carries out these slurries about 2 minutes is used, to remove the bubble in slurry.5 kinds of alumina slurries that the content of obtained alumina particle is different thus.
Next, be one group with 2 described test films, the described alumina slurry of the upper coating of whole of the 20mm × 16mm of a test film wherein, then superposes it in cross mode with 20mm × 16mm face of another test film.Now, the gap of 2 test films is adjusted to about 90 μm, wherein, fills alumina slurry, after the dry evening, obtain interim conjugant.It should be noted that, the alumina content in alumina slurry is that the alumina slurry mobility of 80 quality % is insufficient, can not be applied to test film fully, therefore can not make interim conjugant.
These interim conjugants are transferred in air furnace, to make the face of joined face press as the mode of 0.03MPa is at the upper load alumina sintered body weight of interim conjugant, at 1650 DEG C, burns till 2 hours, obtained aluminum oxide conjugant.Obtained the bar-shaped test film of 3mm × 2mm × 10mm by the aluminum oxide conjugant obtained like this, 3 pliability tests being 8mm by bottom span measure the flexural strength of 3 ~ 4 respectively, calculate mean value.This result is shown in table 1, is studied based on the effect of this result to the alumina content in alumina slurry simultaneously.
Table 1
(result of study)
Make the alumina content in alumina slurry be in the comparative example 1 of 65.0 quality %, when alumina slurry is dry, the steam output of moisture is large, and define large cavity in junction surface, bond strength is obviously deteriorated.On the other hand, the alumina content in alumina slurry is made to be in the comparative example 3 of 80.0 quality %, as mentioned above, the illiquidity of slurry, uncontrollable junction surface thickness, thus interim conjugant can not be obtained.In contrast, the alumina content in alumina slurry is respectively in the embodiment 1 and 2 of 69.5 quality % and 74.5 quality %, the aluminum oxide conjugant that flexural strength is about about 200MPa can manufactured.But, making the alumina content in alumina slurry be in the comparative example 2 of 77.5 quality %, although interim conjugant can be made, and make conjugant by sintering, but as shown in Figure 3, crack 30 at joint interface, only obtain the flexural strength of about 120MPa.As can be known from these results, the alumina content in alumina slurry is greater than 65.0 quality % and is less than 77.5 quality % is suitable.
(research of junction surface thickness)
Alumina content in alumina slurry is fixed as 74.5 quality %, mode same as described above makes aluminum oxide conjugant, difference is, makes the junction surface thickness of interim conjugant be respectively 60 μm, 40 μm, 36 μm, calculates the mean value of 3 flexural strengths.Its result and above-described embodiment 2(junction surface thickness are 90 μm) result be together shown in Table 2, be studied based on the effect of this result to junction surface thickness simultaneously.
Table 2
(result of study)
In thickness at junction surface any one aluminum oxide conjugant in the embodiment 2 ~ 5 of 30 ~ 90 μm of scopes, the sufficient flexural strength of more than 200MPa can both be obtained.It should be noted that, if consider, the thickness at junction surface is less than 30 μm, just can not tackle the concavo-convex of the joined face of alumina sintered body fully, does not therefore make the aluminum oxide conjugant of junction surface thickness less than 30 μm herein.
(research of the face pressure of joined face during sintering)
Alumina content in alumina slurry is fixed as 74.5 quality %, makes the interim conjugant that junction surface thickness is 90 μm.Mode same as described above makes aluminum oxide conjugant, difference is, with make the face of joined face press be respectively 0.015MPa, 0.008MPa, 0MPa(only own wt) mode Supported alumina sintered compact weight on these interim conjugants, calculate the mean value of 3 flexural strengths.The face of its result and above-described embodiment 2(joined face is pressed as 0.03MPa) result be together shown in Table 3, be studied based on the effect of this result to the face pressure of joined face during sintering simultaneously.
Table 3
(result of study)
The face pressure of the joined face when making sintering is in the embodiment 2 and 6 of more than 0.015MPa, can obtain the sufficient flexural strength of more than 200MPa.On the other hand, the face pressure of the joined face when making sintering is that in the comparative example 4 and 5 of below 0.008MPa, flexural strength does not reach 200MPa.It can thus be appreciated that the face pressure making joined face more than load 0.015MPa during sintering is necessary.It should be noted that, in the joint of alumina sintered body being highly more than 1m, inferring that the face of the joined face obtained by own wt is pressed is about 0.04MPa, therefore known, in the joint of this large scale sintering body, also can obtain having the aluminum oxide conjugant of abundant intensity when load does not come from outside loading.
(joint of larger alumina sintered body)
Based on above-mentioned result of study, reference example 2, is used as engaged material and makes aluminum oxide conjugant, in room temperature and 1200 DEG C of air, carried out 4 pliability tests by larger alumina sintered body (block material).Specifically, first, be more than 99.5% by aluminum oxide purity, relative density be more than 99.0% commercial alumina sintered compact be processed into 40mm × 13mm × 20mm, prepare several with wheel grinding 40mm × 13mm face of No. #200 and the test film obtained.Adding in pure water using the mass ratio of 17:1 take ammonium polyacrylate salt as the セ Le Na D305(trade(brand)name that Zhong jing grease company of main component makes as dispersion agent), fully stir, obtained dispersion medium.Relative to this dispersion medium, interpolation purity is more than 99.8%, median size is the alumina particle of 600nm, makes its content be 74.5 quality %, and stirs, thus obtain the slurry that dispersing and mixing in dispersion medium has alumina particle.In addition, the vacuum outgas that vacuum pump carries out these slurries about 2 minutes is used, to remove the bubble in slurry.The content having prepared alumina particle is thus the alumina slurry of 74.5 quality %.
Next, be one group with 2 described test films, the described alumina slurry of the upper coating of whole of the 40mm × 13mm of a test film wherein, then superposes it with 40mm × 13mm face of another test film.Now, the gap of 2 test films is adjusted to about 90 μm, wherein, fills alumina slurry, after the dry evening, obtain the interim conjugant of 40mm × 13mm × 40mm.
This interim conjugant is transferred in air furnace, to make the face of joined face press as the mode of 0.03MPa is at the upper load alumina sintered body weight of interim conjugant, at 1650 DEG C, burns till 2 hours, obtained aluminum oxide conjugant.Obtained with the bar-shaped test film of the JIS R1601 3mm × 4mm × 40mm that is benchmark by the aluminum oxide conjugant obtained like this, carry out 4 pliability tests that bottom span is 30mm, upper span is 10mm.Number for the bar-shaped test film measured is 5 in room temperature flexural test, is 4, calculates mean value respectively in the hot bend test in 1200 DEG C of air.Thus, the calculation result of 4 flexural strengths employed at room temperature with 1200 DEG C of air of the standard test sheet of JIS R1601 is shown in Table 4.
Table 4
As shown in table 4, embodiment 7 average bending strength at room temperature made in the above described manner becomes the high level with the average bending strength same degree of the embodiment 2 shown in table 1.It can thus be appreciated that, even if the size of test film increases also reproducibility can show high strength well.Theoretical according to the ceramics strength of the relation of the size and intensity that discuss test film, it is generally known that along with the increase of test film size, its intensity reduces.This is because compared with little test film, the probability that exists affecting the large crack-like defect of intensity uprises in large test film.But, it is believed that, in the present embodiment, the thick shortcoming that may affect intensity is mainly present in junction surface, and it is believed that, in embodiment 2 and 7, because the thickness at junction surface is identical, the volume that therefore may there is the position of thick shortcoming does not have large difference, result, have nothing to do with the size of test film, almost equal high strength can be obtained.It should be noted that, in embodiment 7, the average bending strength in 1200 DEG C of air also reaches the high level of 157MPa.This is considered to because junction surface is made up of pure alumina sintered body, not containing the equal material making hot strength deterioration of glass.
Industrial applicibility
As described above specific, the present invention relates to the method for joining of aluminum oxide conjugant and alumina sintered body, by the present invention, a kind of test film cut in the mode containing junction surface flexural strength at room temperature can be provided to be more than 200MPa, the conjugant be made up of high-purity alpha-alumina that flexural strength in 1200 DEG C of air is more than 100MPa.The method of joining of the application of the invention, when not needing joined face to have high flat degree, large-scale alumina sintered body can be engaged with each other, in addition, because the constitute at junction surface is only high-purity alpha-alumina, when therefore this conjugant being used for the component parts of various manufacturing installation, the pollution of impurity element can be prevented, the strength deterioration under high temperature can be prevented simultaneously.Due to such feature, the present invention can be used to be provided for requiring the high strength in the large-scale manufacturing installation parts of erosion resistance and thermotolerance and highly purified aluminum oxide conjugant and the alumina sintered body method of joining for the manufacture of this aluminum oxide conjugant.
Nomenclature
1A: interim conjugant
1B: aluminum oxide conjugant
1a, 1b: alumina sintered body
2: junction surface (before sintering)
3: junction surface (after sintering)
20a: do not sinter region
20b: sintering region
20c: thick independent pore
30: crackle
Claims (5)
1. an aluminum oxide conjugant, it is aluminum oxide conjugant alumina sintered body being engaged with each other by junction surface, the aluminum oxide that described junction surface is more than 30 μm by thickness is formed, and by the aperture length on the thickness direction at described junction surface be 40 ~ 100% of the thickness at described junction surface thick independent pore, be do not sinter region and the relative density of the fine pores of less than 5 μm containing aperture be that the sintering region of the densification of more than 98% is formed.
2. aluminum oxide conjugant according to claim 1, use the test film cut from described aluminum oxide conjugant in the mode containing described junction surface, the flexural strength at room temperature measured for benchmark with JIS R1601 is for more than 200MPa, and the flexural strength in 1200 DEG C of air measured for benchmark with JIS R1604 is for more than 100MPa.
3. a duct member, it is the duct member be made up of the aluminum oxide conjugant described in claim 1 or 2, and the compactness alumina sintered body that to have by described junction surface be more than 95% by relative density is engaged with each other the connected structure obtained.
4. duct member according to claim 3, it is used as the component parts of the rotary kiln used in the manufacture of lithium ion secondary battery anode material.
5. the method for joining of an alumina sintered body, it is the method for joining of the alumina sintered body that alumina sintered body is engaged with each other, wherein, to be added with the pure water of dispersion agent as dispersion medium, be prepared in this dispersion medium and be only added with the alumina slurry that obtains as solids component of alumina particle that purity is more than 99.8%, after in the joined face this alumina slurry being applied to described alumina sintered body, joined face is docked each other, the thickness at the junction surface be made up of described alumina slurry between joined face is adjusted to more than 30 μm, directly carry out drying, make interim conjugant, with the face of described joined face pressure for the mode of more than 0.015MPa is to this interim conjugant applying load, in this case, more than 1300 DEG C at the temperature of less than 1700 DEG C, heat-treat in air, sinter described junction surface thus, thus described alumina sintered body is engaged with each other,
The content of the alumina particle in wherein said alumina slurry is greater than 65 quality % and is less than 77.5 quality %.
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| JP2011032863A JP5761636B2 (en) | 2011-02-18 | 2011-02-18 | Joining method of alumina joined body and sintered alumina body |
| JP2011-032863 | 2011-02-18 | ||
| PCT/JP2012/054481 WO2012111854A2 (en) | 2011-02-18 | 2012-02-17 | Alumina conjugate and bonding method for alumina sintered bodies |
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