CN115838280A - Platinum-rhodium alloy plated mullite rotating tube, preparation method and application thereof - Google Patents
Platinum-rhodium alloy plated mullite rotating tube, preparation method and application thereof Download PDFInfo
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- CN115838280A CN115838280A CN202211586236.9A CN202211586236A CN115838280A CN 115838280 A CN115838280 A CN 115838280A CN 202211586236 A CN202211586236 A CN 202211586236A CN 115838280 A CN115838280 A CN 115838280A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
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Abstract
The invention relates to the technical field of glass products, in particular to a platinum-rhodium alloy plated mullite rotary tube, a preparation method and application thereof, and aims to solve the problems that the existing mullite rotary tube is high in porosity and good in thermal shock property, but is easy to generate gas lines. The rotary tube comprises a rotary tube base body and a filler arranged on the rotary tube base body, wherein the filler comprises platinum-rhodium alloy. On one hand: according to the invention, zirconia micro powder is introduced on the basis of a rotating tube substrate, so that the porosity is obviously reduced. On the other hand, after the platinum-rhodium alloy is filled, the density of the rotating pipe matrix is further improved, so that the problem that bubbles are easily caused by the existing rotating pipe can be effectively solved. The synergistic effect of the zirconium oxide, the mullite and the platinum-rhodium alloy can avoid the gas line problem caused by bubbles while keeping the thermal shock performance of the rotating tube.
Description
Technical Field
The invention relates to the technical field of glass products, in particular to a platinum-rhodium alloy plated mullite rotating tube, a preparation method and application thereof.
Background
At present, the rotary tube of the glass kiln is mostly a mullite rotary tube, and the component of the mullite rotary tube is 3Al 2 O 3 ·2Si 2 O 3 The rotary tube is in a honeycomb shape, the thermal shock resistance is good, the working temperature of the rotary tube is 1100-1300 ℃, the working temperature is increased from room temperature to the working temperature when the rotary tube is installed, the mullite porosity is high, the thermal shock resistance is good, but the high porosity can cause bubbles (gas exists in large pores) in the production process of the glass tube, so that gas lines are generated (the bubbles are pulled Cheng Qixian in the tube pulling process), and defects are caused.
Disclosure of Invention
The invention provides a platinum-rhodium alloy plated mullite rotary tube, a preparation method and application thereof, which are used for solving the problems that the existing mullite rotary tube is high in porosity and good in thermal shock property, but is easy to generate gas lines.
In order to alleviate the technical problems, the technical scheme provided by the invention is as follows:
a platinum-rhodium alloy coated mullite rotary tube comprises a rotary tube base body and a filler coated on the rotary tube base body;
the rotary tube substrate comprises the following raw materials in percentage by mass:
20-50 parts of mullite powder;
8-10 parts of talc;
5-8 parts of alumina micro powder;
8-10 parts of silica powder;
10-15 parts of barite;
5-10 parts of zirconia powder;
1-4 parts of sodium hexametaphosphate;
polysorbate 2-8;
a plurality of filling grooves which are arranged at intervals are formed in the surface of the rotary tube base body after the rotary tube base body is sintered and formed, filling materials are filled in the filling grooves, and the filling materials comprise platinum-rhodium alloy.
Further, in the present invention,
the rotary tube substrate comprises the following raw materials in parts by mass:
50 parts of mullite powder;
talc 10;
8, alumina micro powder;
10 parts of silica powder;
10 parts of barite;
zirconia powder 8;
sodium hexametaphosphate 2;
polysorbate 5;
further, in the case of a liquid crystal display device,
the filler further comprises zirconia.
Further, in the present invention,
the sintering temperature is 1400-1500 ℃.
Further, in the case of a liquid crystal display device,
the size of the bottom of the filling groove is the size of the top of the filling groove.
A preparation method of a platinum-rhodium alloy plated mullite rotary tube comprises the following steps:
sintering the rotating tube substrate:
uniformly mixing the following raw materials in parts by mass into slurry:
20-50 parts of mullite powder;
8-10 parts of talc;
5-8 parts of alumina micro powder;
8-10 parts of silica powder;
10-15 parts of barite;
5-10 parts of zirconia powder;
1-4 parts of sodium hexametaphosphate;
polysorbate 2-8;
uniformly mixing raw materials of a rotating tube substrate, extruding the raw materials into a mould, and forming a filling groove on the rotating tube substrate;
filling filler in the filling groove, wherein the filler comprises platinum-rhodium alloy;
and (5) sintering and forming.
Further, in the case of a liquid crystal display device,
the mold is provided with forming teeth, the size of the top of each forming tooth is smaller than that of the bottom of each forming tooth, and filling grooves are formed in the rotary tube base body after the forming teeth are demoulded.
Further, in the present invention,
the filling groove is a dovetail groove.
Further, in the case of a liquid crystal display device,
and a plurality of filling grooves are formed in the surface of the rotating pipe base body at intervals.
An application of a platinum-rhodium alloy coated mullite rotating tube.
The beneficial effects of the invention are analyzed as follows:
the platinum-rhodium alloy plated mullite rotating tube provided by the invention has the advantages that the main matrix is made of mullite, the mullite has more atmospheric holes, and although the atmospheric holes have excellent thermal shock resistance, the problem of bubbles caused by the atmospheric holes in the production process of glass tubes is particularly serious, so that the platinum-rhodium alloy plated mullite rotating tube has the following advantages:
on one hand: the invention introduces zirconia micropowder on the basis of a rotating tube substrate, zirconia only appears in a monoclinic phase at normal temperature, and is converted into a tetragonal phase when heated to about 1100 ℃, and is converted into a cubic phase when heated to a higher temperature. Because the monoclinic phase generates larger volume change when being converted to the tetragonal phase, and the monoclinic phase generates larger volume change in the opposite direction when being cooled, the cracking of the product is easily caused. After the zirconia and the mullite are compounded, the porosity of the rotary pipe can be reduced to a certain extent, and the corrosion resistance of the compounded rotary pipe is much stronger than that of the original rotary pipe due to the strong corrosion resistance of the zirconia. Compared with the existing mullite rotary tube, the rotary tube after being compounded has the advantages that the porosity is obviously reduced, and the gas line problem caused by bubbles in the production process of the glass tube can be effectively avoided after the porosity is reduced.
On the other hand, the platinum-rhodium alloy is filled on the surface of the rotary pipe substrate at intervals, the erosion resistance of the platinum-rhodium alloy is further enhanced compared with that of zirconia, but the linear expansion coefficient of the platinum-rhodium alloy is obviously greater than that of mullite and zirconia, so that the crack is easily expanded and even stripped when the platinum-rhodium alloy is compounded with the rotary pipe substrate under severe extreme cold-extreme thermal conditions (thermal shock). Therefore, the surface of the rotary pipe provided by the invention is provided with a plurality of filling grooves which are arranged at intervals, the platinum-rhodium alloy filler is filled in the filling grooves, and the expansion speed of the platinum-rhodium alloy is higher than that of the rotary pipe base body in the temperature rising process, so that the rotary pipe base body can generate an extrusion effect, the air holes of the rotary pipe base body are reduced, the density of the rotary pipe base body is further improved, and the problem that the conventional rotary pipe is easy to cause bubbles can be effectively solved.
In summary, the synergistic effect of the zirconia, the mullite and the platinum-rhodium alloy can avoid the gas line problem caused by bubbles while maintaining the thermal shock performance of the rotating tube.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention or related technologies, the drawings used in the description of the embodiments or related technologies will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a scanning electron microscope image of F1 in an embodiment of the present invention;
FIG. 2 is a scanning electron microscope image of F7 in an embodiment of the present invention;
FIG. 3 is a cross-sectional view of a rotating tube in an embodiment of the present invention.
Detailed Description
And (2) after the powder is dried and uniformly mixed, adding sodium hexametaphosphate and polysorbate, mixing for 2-3 min, sealing and placing the mixed pug for 24h at normal temperature, pressing the mixture into a 50mm cylindrical sample blank under the pressure of 50MPa, maintaining the mixture for 8h at room temperature, drying the blank, sintering the blank in a high-temperature furnace, preserving the heat, and cooling the blank along with the furnace to obtain a sintered sample.
Watch-rotating tube base batching watch (without filler)
Dial rotary tube batching meter (with filler)
The filler indicated in F6 above is composed of a platinum-rhodium alloy only;
in the above F7, the filler includes platinum-rhodium alloy and zirconia, and the molar ratio of the platinum-rhodium alloy to the zirconia is 1:1.
thermal shock test:
and the thermal shock resistance adopts a rapid cooling and rapid heating circulation method, one end of the standard brick is placed into a furnace and heated to a specified temperature, the standard brick is immediately taken out after being kept warm for a period of time and placed into flowing cold water, and the circulation is repeated until the breakage rate of the tested section reaches 50%. The breakage is represented by the following x, and the breakage rate is not more than 50%, and v represents the breakage rate is 50%.
Results of thermal shock test
The comparison of F1 and F2 experiments shows that: the additive has no influence on the thermal shock property basically, and shows that the additive has no influence on the apparent porosity of the material basically.
In the F3 experiment, after 10 parts of barite and an additive are added, the sample is damaged only by 26 times of cyclic thermal shock, and the thermal shock resistance is obviously improved compared with that of F1 and F2. The mechanism behind is: the barite can partially fill the internal gaps of the mullite to realize partial healing, and in addition, the dispersing effect of the sodium hexametaphosphate as a dispersing agent (additive) and the polysorbate is matched, so that the raw materials can be fully and uniformly mixed in the preparation process, the barite phase is uniformly distributed, and the gaps of the mullite are effectively filled, therefore, the thermal shock resistance is reduced, but the reduction of the porosity is beneficial to reducing the problem of bubbles.
In the F4 experiment, 8 parts of zirconia was added, and the sample broke in 18 thermal cycles, the mechanism behind this being: at normal temperature, zirconia only appears in monoclinic phase, and is converted into tetragonal phase when heated to about 1100 ℃, and is converted into cubic phase when heated to higher temperature. Because the monoclinic phase generates larger volume change when being converted to the tetragonal phase, and the monoclinic phase generates larger volume change in the opposite direction when being cooled, the cracking of the product is easily caused. Cracks are divided into large cracks and into cracks, and the large cracks can cause the sample to be damaged in a thermal shock test. The micro-cracks instead absorb the stress strain, counteracting part of the thermal stress. In the F4 experiment, the thermal shock resistance cannot be obviously improved by simply adding the zirconium oxide.
In the F5 experiment, 10 parts of barite, 8 parts of zirconia and additives are added, and the sample is cracked only after 30 times of thermal cycles, which shows that the F5 sample has better thermal shock resistance. The mechanism behind is: the barite fills the mullite gaps, the zirconia phase transformation does not bring large cracks but brings microcracks, and the balance of the deformation amount and cracks of the zirconia is obtained in the F5 sample. The microcracks absorb the stress strain and counteract a portion of the thermal stress, thereby significantly improving thermal shock resistance.
Porosity test
In the example, the samples were tested for apparent porosity and bulk density, and the experiment was carried out according to GB7321-2004 "method for preparing samples of shaped refractory articles" to prepare the required samples, and according to GB/T2997-2000 "method for testing volume density, apparent porosity and true porosity of densely shaped refractory articles".
Table four porosity experimental results
| F1 | F2 | F3 | F4 | F5 | F6 | F7 | |
| Apparent porosity% | 18.74 | 18.51 | 17.61 | 17.54 | 16.21 | 15.41 | 14.93 |
The porosity experiment shows that: the porosity was reduced by adding barite and zirconia, and particularly by adding barite and zirconia together, the porosity was reduced to 16.21%. When the platinum-rhodium alloy or the mixture of the platinum-rhodium alloy and the zirconia is filled, the porosity is respectively reduced to 15.41 percent and 14.93 percent, and the porosity is greatly reduced. The above porosity test results correspond to the thermal shock results.
In F6: the anti-erosion capability of the platinum-rhodium alloy is obviously higher than that of zirconia and mullite, that is, the anti-erosion capability of the rotating pipe added with the platinum-rhodium alloy on the surface is obviously higher than that of the existing mullite rotating pipe or zirconia-corundum rotating pipe. However, there is a problem that the platinum-rhodium alloy is easily cracked and peeled off from the substrate under severe extreme cold and extreme hot conditions, and therefore, in order to fully utilize the corrosion resistance of the platinum-rhodium alloy and improve the bonding ability between the platinum-rhodium alloy and the substrate:
the rotary tube is provided with a plurality of filling grooves which are arranged at intervals on the surface, the platinum-rhodium alloy filler is filled in the filling grooves, and in the temperature rise process, the expansion speed of the platinum-rhodium alloy is higher than that of the rotary tube substrate, so that an extrusion effect can be generated on the rotary tube substrate, the air holes of the rotary tube substrate are reduced, and the density of the rotary tube substrate is improved. In an alternative of this embodiment, it is preferable that the filling grooves are arranged in a dovetail groove structure, and the plurality of filling grooves are arranged around the surface of the rotating pipe at intervals in various manners, such as uniformly spaced around the rotating pipe, or at uniformly spaced spiral positions. With regard to the shape and structure of the filling grooves, see in particular fig. 3.
In F7, the filler comprises platinum-rhodium alloy and zirconia, and the molar ratio of the platinum-rhodium alloy to the zirconia is 1:1. after the zirconia is added, the zirconia can be fully fused with the zirconia in the matrix in the sintering process, so that the fusion degree of the interface is improved, and the stripping problem caused in the thermal shock process is further avoided. Referring to fig. 1, fig. 1 is a scanning electron micrograph of F1, wherein the surface of the rotating tube has larger pores, fig. 2 is a scanning point of F7 showing a current day diagram, in which large crystals of the filler are shown and the surface is denser. The scanning electron microscope result corresponds to the porosity and thermal shock experimental result.
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A platinum-rhodium alloy coated mullite rotating tube is characterized in that: the device comprises a rotating tube substrate and a filler coated on the rotating tube substrate;
the rotary tube substrate comprises the following raw materials in percentage by mass:
20-50 parts of mullite powder;
8-10 parts of talc;
5-8 parts of alumina micro powder;
8-10 parts of silica powder;
10-15 parts of barite;
5-10 parts of zirconia powder;
1-4 parts of sodium hexametaphosphate;
polysorbate 2-8;
a plurality of filling grooves which are arranged at intervals are formed in the surface of the rotary tube base body after sintering and forming, filling materials are filled in the filling grooves, and the filling materials comprise platinum-rhodium alloy.
2. The platinum rhodium alloy-plated mullite swivel tube of claim 1, wherein:
the rotary tube substrate comprises the following raw materials in percentage by mass:
50 parts of mullite powder;
talc 10;
8, alumina micro powder;
10 parts of silica powder;
barite 10;
zirconia powder 8;
sodium hexametaphosphate 2;
polysorbate 5.
3. The platinum rhodium alloy-plated mullite swivel tube of claim 1, wherein:
the filler also includes zirconia.
4. The platinum rhodium alloy-plated mullite swivel tube of claim 1, wherein:
the sintering temperature is 1400-1500 ℃.
5. The platinum rhodium alloy-plated mullite swivel tube of claim 1, wherein:
the size of the bottom of the filling groove is the size of the top of the filling groove.
6. A preparation method of a platinum-rhodium alloy plated mullite rotary tube is characterized by comprising the following steps: the method comprises the following steps:
sintering the rotating tube substrate:
uniformly mixing the following raw materials in parts by mass into slurry:
20-50 parts of mullite powder;
8-10 parts of talc;
5-8 parts of alumina micro powder;
8-10 parts of silica powder;
10-15 parts of barite;
5-10 parts of zirconia powder;
1-4 parts of sodium hexametaphosphate;
polysorbate 2-8;
uniformly mixing raw materials of a rotating tube substrate, extruding the raw materials into a mould, and forming a filling groove on the rotating tube substrate;
filling filler in the filling groove, wherein the filler comprises platinum-rhodium alloy;
and (5) sintering and forming.
7. The method for preparing the platinum-rhodium alloy plated mullite rotary tube as claimed in claim 6, wherein:
the mold is provided with forming teeth, the size of the top of each forming tooth is smaller than that of the bottom of each forming tooth, and filling grooves are formed in the rotary tube base body after the forming teeth are demoulded.
8. The method for preparing a platinum-rhodium alloy-plated mullite rotary tube as claimed in claim 7, wherein:
the filling groove is a dovetail groove.
9. The method for preparing a platinum-rhodium alloy-plated mullite rotary tube as claimed in claim 8, wherein:
a plurality of filling grooves are formed in the surface of the rotating tube base body at intervals.
10. An application of a platinum-rhodium alloy coated mullite rotating tube.
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| CN202211586236.9A CN115838280B (en) | 2022-12-09 | 2022-12-09 | Platinum-rhodium alloy plated mullite rotary tube, preparation method and application thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1179405A (en) * | 1997-11-04 | 1998-04-22 | 胡勇波 | Zirconium magnesium tempering porcelain |
| JP2008121073A (en) * | 2006-11-13 | 2008-05-29 | Asahi Glass Co Ltd | Electrocast brick with metal film and production method therefor |
| CN107721445A (en) * | 2017-11-16 | 2018-02-23 | 成都市丹炉高温科技有限责任公司 | A kind of high-strength mullite pouring material preparation method |
| WO2019008270A1 (en) * | 2017-07-03 | 2019-01-10 | Sarp Industries | Refractory material comprising a mullite-zirconia matrix with additives |
| CN110790485A (en) * | 2019-08-30 | 2020-02-14 | 醴陵旗滨电子玻璃有限公司 | Glass tube forming device and glass tube forming system |
| CN114988894A (en) * | 2022-06-07 | 2022-09-02 | 湖南旗滨医药材料科技有限公司 | Light thermal shock-resistant mullite cordierite rotary tube and preparation method thereof |
-
2022
- 2022-12-09 CN CN202211586236.9A patent/CN115838280B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1179405A (en) * | 1997-11-04 | 1998-04-22 | 胡勇波 | Zirconium magnesium tempering porcelain |
| JP2008121073A (en) * | 2006-11-13 | 2008-05-29 | Asahi Glass Co Ltd | Electrocast brick with metal film and production method therefor |
| WO2019008270A1 (en) * | 2017-07-03 | 2019-01-10 | Sarp Industries | Refractory material comprising a mullite-zirconia matrix with additives |
| CN107721445A (en) * | 2017-11-16 | 2018-02-23 | 成都市丹炉高温科技有限责任公司 | A kind of high-strength mullite pouring material preparation method |
| CN110790485A (en) * | 2019-08-30 | 2020-02-14 | 醴陵旗滨电子玻璃有限公司 | Glass tube forming device and glass tube forming system |
| CN114988894A (en) * | 2022-06-07 | 2022-09-02 | 湖南旗滨医药材料科技有限公司 | Light thermal shock-resistant mullite cordierite rotary tube and preparation method thereof |
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