阅读说明：本技术 一种Ti-Ti5Si3多孔内壁梯度膜管制备方法及其应用 (A kind of Ti-Ti5Si3Porous internal walls Gradient Film tube preparation method and its application ) 是由 刘渊 刘忠军 荆远 刘卓萌 姬帅 于 2019-08-23 设计创作，主要内容包括：本发明提供了一种Ti-Ti_5Si_3多孔内壁梯度膜管制备方法及其应用,该Ti-Ti_5Si_3多孔内壁梯度膜管的制备方法制得的Ti-Ti_5Si_3多孔内壁梯度膜管,包括外部支撑层和内壁精度控制层,其特征主要在于利用限域内反应烧结获得内壁Ti_5Si_3多孔精度控制层。本发明所涉及的梯度膜管制备方法制备多孔膜管成型过程一次成型,成品率高,在保证过滤管高过滤精度的同时,可以根据需求改变支撑层钛金属粉末的粒度组成实现该内壁梯度膜管的过滤通量调整。该新型过滤管可以应用在高端生物医药、污水处理、海水前级净化等领域,具有巨大的市场应用价值和潜力。(The present invention provides a kind of Ti-Ti 5 Si 3 Porous internal walls Gradient Film tube preparation method and its application, the Ti-Ti 5 Si 3 Ti-Ti made from the preparation method of porous internal walls gradient membrane tube 5 Si 3 Porous internal walls gradient membrane tube, including outer standoff layer and inner wall precision controlling layer, which is mainly characterized in that obtaining inner wall Ti using reaction-sintered in confinement 5 Si 3 Porous precision controlling layer.Gradient Film tube preparation method according to the present invention prepares porous membrane tube forming process one-pass molding, high yield rate, while guaranteeing screen pipe high filtering precision, the filtration flux adjustment of the inner wall gradient membrane tube is realized in the granularmetric composition that can change supporting layer titanium metal powder according to demand.The Novel filtration pipe can be applied in fields such as high-end biological medicine, sewage treatment, the purifications of seawater prime, have huge market application value and potentiality.)

1. a kind of Ti-Ti₅Si₃Porous internal walls Gradient Film tube preparation method, it is characterised in that steps are as follows:

(1) the Ti powder in the certain particle size section being sieving through is subjected to gradation as desired, is uniformly mixed；

(2) molding die is got out, gum cover and plug are fixed, plug is process by high purity quartz；

(3) powder of certain mass in step (1) is weighed first, then charging forming；

(4) porous membrane tube semi-finished product obtained in (3) are put into compression moulding in cold isostatic press, pressing pressure 40-180MPa；

(5) the Ti porous membrane tube green compact that (4) obtain are demoulded, retains high purity quartz rigidity plug；

(6) it is put into vacuum drying oven and is sintered together with high purity quartz rigidity plug through Ti porous membrane tube green compact obtained in (5), vacuum degree Higher than 5 × 10^-2Pa, heating rate are 1~10 DEG C/min, and sintering temperature is 650~1000 DEG C, keeps the temperature 0.5~3 hour, cooling Porous filtering pipe is separated with high purity quartz rigidity plug afterwards, obtains Ti-Ti₅Si₃Porous internal walls gradient membrane tube；In this step Reaction-sintered in confinement occurs, following reaction mainly occurs in sintering process:

3SiO₂+8Ti-→Ti₅Si₃+3TiO₂。

2. Ti-Ti according to claim 1₅Si₃Porous internal walls Gradient Film tube preparation method, it is characterised in that molding die Middle selection high purity quartz stick is as rigid plug, and high purity quartz stick is sintered together with Ti porous filtering pipe green compact when sintering, this mistake Journey high purity quartz stick provides silicon source, generates Ti in Ti porous filter core inner surface reaction-sintered₅Si₃Porous gradient film.

3. Ti-Ti according to claim 1₅Si₃Porous internal walls Gradient Film tube preparation method, it is characterised in that its sintered bar Part is vacuum.

4. a kind of use Ti-Ti as described in claim 1₅Si₃The application of porous internal walls Gradient Film tube preparation method, feature It is: realizes preparation Ti-TiSi porous internal walls gradient membrane tube, Ti-TiSi₂Porous internal walls gradient membrane tube and Ti-Ti₅Si₄It is porous Inner wall Gradient Film tube material, react involved in sintering process has respectively:

SiO₂+2Ti———→TiSi+TiO₂

2SiO₂+3Ti———→TiSi₂+2TiO₂

4SiO₂+9Ti———→Ti₅Si₄+4TiO₂。

Technical field

The present invention relates to a kind of porous gradient membrane tubes and preparation method thereof, and in particular to a kind of Ti-Ti₅Si₃Porous internal walls ladder Spend membrane tube preparation method and applications.

Background technique

The feature that there is the porous based composites of graded metal aperture size or porosity to change in gradient, compared to homogeneous Porous material, it has more excellent performance.With the high speed development of industry, the requirement to porous material is also higher and higher, In application, more to be separated by filtration field particularly true: while it requires material to have more small pore size, also requiring material With higher filtering accuracy and bigger transmitance, this makes traditional homogeneous porous material be difficult to reach expected requirement, and The appearance of gradient porous material can be very good to solve this contradiction.Graded metal porous material has asymmetric apertures structure, i.e., Aperture or porosity through-thickness change in gradient, are also unsymmetrical metal porous material or microporous metal membrane, it can be same The small-bore Shi Shixian and big transmitance, filtering accuracy and filter efficiency can be greatlyd improve in the field of being separated by filtration by applying.

Can be used for industrial powder sintered inorganic porous material both at home and abroad at present includes ceramic porous material and metal Porous material.Preparation for these two types of porous materials, the formation of hole be mainly derived between raw material powder it is existing between Gap and in advance addition pore creating material and the process removed.Ceramic porous material has the performances such as high temperature high voltage resistant and corrosion resistant candle, but Its room-temperature mechanical property, welding performance and leakproofness are insufficient, restrict its application field.And metal polyporous material is then on the contrary, tool Standby preferable room-temperature mechanical property and it is dry connect, sealing performance, but since the characteristic of metal material itself leads to existing be prepared into Type technique cannot obtain high-precision (filtering accuracy is greater than 0.1um) metal porous membrane material, to limit metal polyporous material In the application of every field.

In view of the above-mentioned problems, the porous ceramic film material with gradient aperture structure is developed developed first, by one The research and development fixed time is widely used in fields such as energy environment protection, medicine, chemical industry, thermal barrier coatings.But ladder Spend porous ceramic film material there are a series of deficiency, such as preparation and sintering process relative difficulty, cost is relatively expensive and easy production Raw defect.Therefore people start to find and prepare the material with gradient porous structure in metal material field and expand its application Range and improve its filtering accuracy and filter efficiency.With the research and development of gradient aperture porous metals-ceramics, the knot of porous material Structure is further improved with application.

A kind of patent of invention (CN108188403A) " Ti-Ti₅Si₃The preparation method of complex gradient porous membrane tube " discloses A kind of Ti-Ti₅Si₃The preparation method of complex gradient porous membrane tube, this method proposition use pyroceram as the outer of molding die Just set, can prepare Ti-Ti by this method₅Si₃Complex gradient porous membrane tube, the gradient membrane tube gradient film is in porous membrane tube Outer surface, be not directed to gradient membrane tube gradient layer in the preparation and preparation method of inner surface, there is certain application limitation. The invention patent is effective supplement of preparation process involved in this patent of invention and method, can greatly extend such product The type of material and its application range.

The invention patent is quasi- by the limited sintering of material interface, between film layer itself sintering grow and rigid plug Compression inhibits interface stress to concentrate, by anti-between high-purity quartz rigidity plug and metal porous Titanium base in confinement It should be sintered, realize Ti-Ti₅Si₃The molding and preparation of porous internal walls gradient membrane tube.The Ti-Ti prepared by this patent₅Si₃It is porous The military service performance of metal-ceramic gradient porous material can be improved in inner wall gradient membrane tube, and extend such existing material uses model It encloses, such as there is high filtering precision performance to have both big flux, can apply net in high-end biological medicine, sewage treatment, seawater prime The fields such as change have huge market application value and potentiality.

Summary of the invention

The object of the present invention is to provide a kind of Ti-Ti of suitable large-scale production₅Si₃The standby side of porous internal walls Gradient Film control Method and its application.

The technical solution adopted by the present invention relates generally to a kind of Ti-Ti₅Si₃Porous internal walls Gradient Film tube preparation method, specifically Steps are as follows:

(1) the Ti powder in the certain particle size section being sieving through is subjected to gradation as desired, is uniformly mixed；

(2) molding die is got out, gum cover and plug are fixed, plug is process by high purity quartz；

(3) powder of certain mass in step (1) is weighed first, then charging forming；

(4) porous membrane tube semi-finished product obtained in (3) are put into compression moulding in cold isostatic press, pressing pressure 40- 180MPa；

(5) the Ti porous membrane tube green compact that (4) obtain are demoulded, retains high purity quartz rigidity plug；

(6) it is put into vacuum drying oven and is sintered together with high purity quartz rigidity plug through Ti porous membrane tube green compact obtained in (5), very Reciprocal of duty cycle is higher than 5 × 10^-2Pa, heating rate are 1~10 DEG C/min, and sintering temperature is 650~1000 DEG C, keep the temperature 0.5~3 hour, Porous filtering pipe is separated with high purity quartz rigidity plug after cooling, obtains Ti-Ti₅Si₃Porous internal walls gradient membrane tube.This step Reaction-sintered in confinement occurs in rapid, following reaction mainly occurs in sintering process:

3SiO₂+8Ti-→Ti₅Si₃+3TiO₂。

It is improved as the first step of the invention, is to select the conduct of high purity quartz stick in molding die in the step (5) Rigid plug, high purity quartz stick is sintered together with Ti porous filtering pipe green compact when sintering, this process high purity quartz stick provides silicon source, Ti is generated in Ti porous filter core inner surface reaction-sintered₅Si₃Porous gradient film.

It is improved as second step of the invention, the sintering atmosphere of the confinement reaction sintering technology in the step (6) is true It is empty.

It is improved as third step of the invention, the gradient porous membrane tube preparation method of the metal-ceramic is not limited to preparation Ti- Ti₅Si₃Porous internal walls gradient membrane tube, this method can also realize preparation Ti-TiSi porous internal walls gradient membrane tube, Ti-TiSi₂It is more Hole inner wall gradient membrane tube and Ti-Ti₅Si₄Porous internal walls Gradient Film tube material, react involved in sintering process has respectively:

SiO₂+2Ti---→TiSi+TiO₂

2SiO₂+3Ti---→TiSi₂+2TiO₂

4SiO₂+9Ti---→Ti_SSi₄+4TiO₂

It is a kind of according to the Ti-Ti₅Si₃Ti-Ti made from porous internal walls Gradient Film tube preparation method₅Si₃Porous internal walls ladder Membrane tube, including metal powder matrix and inner wall precision controlling layer are spent, essentially consists in gradient porous membrane tube sintering process using confinement Interior reaction sintering technology.

A kind of Ti-Ti₅Si₃The molding die of porous internal walls Gradient Film tube preparation method, including metal powder, high purity quartz Rigid plug, reaction equation are as follows: 3SiO₂+8Ti-→Ti₅Si₃+3TiO₂。

The screening of powder particle is to prepare an important link of metal polyporous material.Prepare common metal porous material When, the powder of certain granules size distribution, the bulky grain in this usual polyporous materials are selected according to the requirement of strainability It is mixed in a jumble with little particle, the sintering shrinkage of such material various pieces in sintering is basically the same, material Sintering warpage is less likely to occur, but the high filtering accuracy of homogeneous metal porous material and high through performance cannot reach simultaneously. The technology path key that this method is related to is: the powder of narrower particle size distribution is obtained by screening, in above-mentioned material charging forming mistake The outer layer of Cheng Zhong, Ti powder is surrounded by the rigid set of gum cover, hole on steel bushing, and forming core rod is high-purity quartz rigidity plug, so The special sintering technique being related to afterwards using this method finally realizes the preparation of finished product porous internal walls gradient membrane tube.Reaction is burnt in confinement Knot technique largely solves ceramic film and metal material matrix the interlayer ladder because caused by being concentrated interface stress Spend the problems such as layer combines insecure, sintering warpage, film layer peeling.

The present invention improves the air transmission coefficient of membrane tube while guaranteeing metal porous inner wall gradient membrane tube filtering accuracy； The Ti-Ti of preparation₅Si₃The once sintered molding of porous internal walls gradient membrane tube is produced in batches at low cost.

Below by drawings and examples, the present invention is described in further detail.

Detailed description of the invention

Fig. 1 is mold structure diagram involved in this patent；

Fig. 2 is the rigid nested structure schematic diagram of molding involved in this patent；

Fig. 3 is Ti-Ti₅Si₃The cross section structure schematic diagram of porous internal walls gradient membrane tube；

Fig. 4 is Ti-Ti₅Si₃Porous internal walls Gradient Film pipe surface SEM photograph；

Fig. 5 is Ti-Ti₅Si₃Porous internal walls Gradient Film tube section SEM photograph；

Wherein: 1, molding just covers；2, gum cover；3, seal rubber plug；4, metal powder；5, high purity quartz rigidity plug；6, block Hoop；7, metal powder matrix；8, inner wall precision controlling layer.

Specific embodiment