CN102352143A - Glass coating and film technology for reducing platinum rhodium alloy bushing plate loss - Google Patents
Glass coating and film technology for reducing platinum rhodium alloy bushing plate loss Download PDFInfo
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- CN102352143A CN102352143A CN2011101776355A CN201110177635A CN102352143A CN 102352143 A CN102352143 A CN 102352143A CN 2011101776355 A CN2011101776355 A CN 2011101776355A CN 201110177635 A CN201110177635 A CN 201110177635A CN 102352143 A CN102352143 A CN 102352143A
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Abstract
A glass coating for reducing platinum rhodium alloy bushing plate loss provided by the invention comprises glass and Suzhou soil in a mass ratio of 9-15:1; a film technology employs a sol-gel film method, which is simple; and the coating raw material is cheap and with a utilization rate. Small size (nanometer level) oxide particles with high specific surface area and high activity can be obtained; and the coating has high uniformity, and multiple ingredient uniform oxide coating is easily prepared.
Description
Technical field
The present invention relates to a kind of high temperature resistantly, anti-washing away, and glass coating composition simple to operate are promptly reduced the glass coating and the coating process of the loss of platinum rhodium bushing.
Background technology
The content of platinum metals in ore is generally very low, only several grams per ton.The platinum rhodium metal is one of extremely short strategic resource of China.Platinum rhodium precious metal is with its high temperature resistant erosion; Has good oxidation-resistance under the high temperature; Creep resistance under the high temperature resistance loading condition; Little to the glass metal wetting angle, such performance and being widely used in the production of glass fiber industry.
Noble metal price on the world market continues soaring, platinum wherein, and the price of rhodium reached respectively to 300,000 yuan/kilogram and 1,420,000 yuan/kilogram of record-breaking month average prices in May in this year.Glass fibre factory invests greatly and is used to buy platinum rhodium precious metal.Owing to be under the hot conditions for a long time, the easy oxidation of platinum rhodium forms oxide compound and volatilizees from the surface of metal exposed, and the someone studies rhodium loss aborning greater than platinum.
Glass fibre is to produce to be mainly used in the matrix material, the application of the performance that the glass fiber compound material instrument is excellent more and more widely, this causes the output of glass fibre to increase.Therefore it is imperative to reduce in the glass fibre production process volatilization of platinum rhodium.Someone attempts to make bushing with substitute material, but has all failed.Its reason is that these bushing manufacturing expenses are expensive, and work-ing life is very short.Therefore increase the cost that glass fibre is made, and reduced quality product.Yet the research of seeking substitute material does not stop.The work of having delivered recently is to coat stainless steel with platinum to make bushing, and leting slip a remark of processing of platinum pipe is embedded in the eyelet that punching press forms in the base plate, and through isobaric consolidation, but effect is not very desirable.It seems that at present it is inevitable that glass fiber industry is used the platinum rhodium metal.
Engineering ceramics has excellent chemical stability; High temperature oxidation resistance and heat-proof quality; Utilize these characteristics; Adopt heat spraying method engineering ceramics to be sprayed on the surface of metal works as coated material; Material is anti-corrosion, wear-resisting to improve, oxidation-resistance and heat-proof quality; On engineering, to use, yet anti-corrosion, wear-resisting, resistance to oxidation and heat-proof quality are often with the Working environment of temperature rapid heat cycle at present.Therefore, the quality of coating thermal-shock resistance thermal shock resistance also is to give full play to the above-mentioned characteristic of coated material, makes ceramic coating on engineering, be able to the key of widespread use.According to reported in literature; Research to the coating thermal shock resistance mainly is below 850 ℃ at present; Under this study condition; The height of the viewpoint that the person of being studied generally acknowledges---coating thermal shock resistance depends primarily on not matching of the coating and the matrix coefficient of expansion; Based on this view; Industry is at present gone up and is selected to bear the ceramic layer of thermal shocking, all adopts and the comparatively close ZrO of the metallic matrix coefficient of expansion
2As spray material, but ZrO
2The spraying powder costs an arm and a leg the cost of workpiece is obviously raise.Apply one deck glass-ceramic in the metallic surface and can reduce the metal meter and carry and the contacting of outside air, well protected metal, this reduces the platinum rhodium and at high temperature volatilizees a kind of thinking is provided for we study.
Summary of the invention
The present invention is in view of above situation, designs, tested a kind of high temperature resistant, and anti-washing away, and glass coating composition simple to operate are promptly reduced the glass coating and the coating process of the loss of platinum rhodium bushing, and it can be used for reducing the loss of platinum rhodium bushing.
The selection of coating ingredients is inertia melt film shield type protection mechanism based on coating system to the provide protection of matrix; The cohesive action of melten glass phase makes coating and matrix bond during high temperature; The hole that blocks coating makes coating more closely knit; Stop or slow down diffusion process; Reduce the erosion of corrosive medium, to reach the purpose of protection matrix to matrix.The glass frit material is as cakingagent, and admixture Suzhou soil causes coating to peel off from matrix in order to regulate the high-temperature viscosity and the coating property of coating when preventing too much glassy phase chilling.
The glass coating of reduction platinum rhodium bushing provided by the invention loss is to be become with Suzhou local soil type by glass ingredient, and the part by weight of glass ingredient and Suzhou soil is 9-15:1.Preferably, the part by weight of glass ingredient and Suzhou soil is 9-11:1.Preferred part by weight is 9,11,13 or 15:1.
Described glass coating, preferred scheme is that the composition of said glass ingredient is: 45～55 parts SiO
2, 35～45 parts Al
2O
3, 6～12 parts Na
2O, CaO are 1～4 part, and MgO is 0.5～3 part, 0.1～0.6 part Li
2O, 0～1 part La
2O
3, be weight part.
Aforesaid glass coating, preferred scheme is SiO
2Be 47～51 parts, Al
2O
3Be 35～38 parts, Na
2O is 6～10 parts, and CaO is 1.5～3 parts, and MgO is 1～2.5 part, Li
2O is 0.3～0.5 part, La
2O
3It is 0.5～0.8 part.
Described glass coating, preferred scheme is that CaO is 1～4 part.
The coating process of the glass coating of reduction platinum rhodium bushing provided by the invention loss, step is following:
(1) colloidal sol preparation: it is native to take by weighing glass ingredient and Suzhou in proportion, mixes to transparently with deionized water, dehydrated alcohol, takes out behind the 32-37 ℃ of water-bath 4-8h, and room temperature preservation is for use;
(2) bushing coating: earlier bushing is cleaned, clean with alcohol, on sol evenning machine, film, the colloidal sol for preparing is dropped in the center that rotates sample, colloidal sol is even film forming under action of centrifugal force;
(3) sample of will filming is put into resistance furnace and is dried, and accomplishes and films for the first time, repeats above-mentioned steps, and sample is carried out filming the second time.
Described coating process, preferred scheme is that step (1) will be stirred to transparent colloidal sol and behind 35 ℃ of water-bath 6h, take out, room temperature preservation is for use.
Described coating process, preferred scheme is that dryer is made as: 3 ℃/min in 0～200 ℃ of scope, 5 ℃/min in 200～1400 ℃ of scopes, insulation 2h when temperature rises to 1400 ℃.
Described coating method, preferred scheme is, picks an amount of colloidal sol wiping sample edges and corners and uncoated place gently with absorbent cotton after the film forming of step (2) sample two sides, makes it form uniform coating.
In the present invention, SiO
2Mainly play the glass network skeleton, can reduce the thermal expansivity of glass, improve the thermostability of glass, thermotolerance.But during too high levels, can significantly improve glass melting temperature, and possibly cause crystallization.Al
2O
3Belong to intermediate oxide, content surpasses certain limit, and glass metal viscosity can increase.Al
2O
3Work to suppress phase-splitting, improve chemical stability, the thermostability of glass.Na
2O is the glass network ectosome, and sodium ion occupy in the hole of glass structure, Na
2O can provide free oxygen to make O/Si ratio increase in the glass structure, scission of link takes place, thereby can reduce the viscosity of glass, makes glass be easy to fusion, is the good solubility promoter of glass, Na
2O can not introduce too much.Na in this glass ingredient
2O and Al
2O
3Molecular ratio greater than 1, Al
2O
3Form aluminum-oxygen tetrahedron and form successive structure net, improved the thermostability and the thermal expansivity of coating with silicon-oxy tetrahedron.CaO mainly plays the effect of stability, reduces the viscosity of glass during high temperature, promotes the fusing and the clarification of glass, and when CaO content was higher, the devitrification of glass tendency increased, and when therefore CaO content was 1～5 part in this glass system, effect was comparatively superior.MgO is a network outer body, can improve the formation performance of glass, reduces the tendency towards devitrification and the crystallization velocity of glass, improves the performance of glass, and MgO can replace proper C aO to improve the performance of glass coating, and when the replacement amount was 1～2.5 part, effect was superior.Li
2It has the intensive fluxing action O, introduces as neccessary composition, and form that can triphane is introduced, and also can introduce by purifying worker raw material.
Suzhou soil causes coating to peel off from matrix in order to regulate the high-temperature viscosity and the coating property of coating when preventing too much glassy phase chilling, and it originates in Yangshan, Suzhou, Jiangsu Province, China one band, hence obtains one's name.Two types of craft and mechanical beneficiations are arranged, high-quality product, outward appearance is white in color, and the quality exquisiteness is lubricious, and burning the back whiteness can reach more than 90%, so have another name called the Suzhou carclazyte.High-quality Suzhou soil is commonly used manual selected and get, impurity seldom, essential mineral is tubulose halloysite and sheet kaolinite, is natural high quality raw material rare in the special cermacis.The Suzhou contained essential substance alumina content of soil is 37%～39%, silicon-dioxide 46%～48%, and 1730 ℃ of refractoriness, plasticity-is lower, mainly is used for making pottery, also can be used as the wedding agent of refractory materials.
To the characteristics of coating for metal surfaces complicated operation, the present invention adopts the sol gel spin coating method, and this method equipment and technology are simple, and coating is high with low in raw material cost and utilization ratio; Can obtain small size (nano level) oxide particle, have high-specific surface area and high activity; The coating uniformity coefficient is high, is prone to make the even oxide coating of polycomponent.
In addition, technology of the present invention also is embodied in:
1, under hot conditions, glass coating and platinum rhodium bushing interface bonded problem have been solved.
2, the glass coating that is coated in platinum rhodium bushing surface has not only obviously reduced the volatilization of platinum rhodium noble metal, and can not influence the production technique of glass fibre.
Embodiment
List specific embodiment below with the technical scheme in further explanation and the explanation this patent, but and not only be confined to this.
Embodiment is raw materials used all can be bought from market,, goes up from apparent available from Shenyang Yin Shan kaolin company limited such as used Suzhou soil, and Suzhou soil presents little red, white or yellow more.Calcic is more in the soil of yellow Suzhou, and Chang Hantie is more in the soil of little red Suzhou, and production is disadvantageous to glass fibre.In the present invention, adopt white Suzhou soil.
The platinum rhodium bushing is one of main device during glass fibre is produced; Be shaped as a grooved container; Melten glass flows into bushing in drawing process; By it it is modulated to suitable temp; Be stretched as continuous glass fibre then through the outflow of leting slip a remark on the base plate, and in the exit by the drawing wire machine of high speed rotating.Wherein the loss amount in 1 year of platinum rhodium bushing work of 6kg is about 60g, but the gained data significantly are lower than this among the embodiment.
Embodiment 1, the glass coating and the coating process of the loss of reduction platinum rhodium bushing
The preparation of colloidal sol: the mass ratio by 15:1 takes by weighing glass chemistry component and white Suzhou soil, and with sub-water, dehydrated alcohol mixing stirring, stirred solution takes out behind 35 ℃ of water-bath 6h to transparent, and room temperature preservation is for use.The glass chemistry component amount of taking by weighing is like table 1:
Table 1 glass chemistry component (weight part)
| The experiment number | 1 | 2 | 3 | 4 | 5 | 6 |
| SiO 2 | 45 | 47 | 49 | 51 | 53 | 55 |
| Al 2O 3 | 39.5 | 38 | 37.5 | 37 | 35.5 | 35 |
| Na 2O | 11.5 | 10.5 | 8.5 | 7.5 | 6.5 | 6 |
| CaO | 2 | 2.1 | 1.9 | 2.2 | 1.5 | 1 |
| MgO | 1.2 | 1.3 | 1 | 1.1 | 2.4 | 2 |
| Li 2O | 0.3 | 0.5 | 0.4 | 0.5 | 0.3 | 0.4 |
| La 2O 3 | 0.5 | 0.6 | 0.7 | 0.7 | 0.8 | 0.6 |
The sample of will filming is put into the self-control resistance furnace dries, and dryer is made as: 3 ℃/min in 0～200 ℃ of scope, and 5 ℃/min in 200～1400 ℃ of scopes, temperature is incubated 2 h when rising to 1400 ℃.More than, repeat above-mentioned steps, sample is carried out filming the second time for filming for the first time.
According to aforesaid operations, preparation platinum rhodium bushing coating.After the bushing work 1 year, dismounting is weighed, and concrete outcome is as shown in table 2.
Table 2 bushing loss amount/g
| The experiment number | 1 | 2 | 3 | 4 | 5 | 6 |
| Loss amount | 55.2 | 51.2 | 49.4 | 52.6 | 55.7 | 57.3 |
Embodiment 2, take by weighing glass chemistry component and white Suzhou soil by the mass ratio of 13:1, take by weighing the glass chemistry component according to table 1, experiment number is 7,8,9,10,11,12.Practical implementation method and embodiment 1 are same, and bushing work is after 1 year, and dismounting is weighed, and concrete outcome is as shown in table 3.
Table 3 bushing loss amount/g
| The experiment number | 7 | 8 | 9 | 10 | 11 | 12 |
| Loss amount | 40.7 | 31.5 | 33.2 | 35.8 | 36.5 | 43.6 |
Embodiment 3, take by weighing glass chemistry component and white Suzhou soil by the mass ratio of 11:1, take by weighing the glass chemistry component according to table 1, experiment number is 13,14,15,16,17,18.Practical implementation method and embodiment 1 are same, and bushing work is after 1 year, and dismounting is weighed, and concrete outcome is as shown in table 4.
Table 4 bushing loss amount/g
| The experiment number | 13 | 14 | 15 | 16 | 17 | 18 |
| Loss amount | 29.4 | 31.3 | 26.5 | 27.7 | 25.2 | 30.1 |
Embodiment 4, take by weighing glass chemistry component and white Suzhou soil by the mass ratio of 9:1, take by weighing the glass chemistry component according to table 1, experiment number is 19,20,21,22,23,24.Practical implementation method and embodiment 1 are same, and bushing work is after 1 year, and dismounting is weighed, and concrete outcome is as shown in table 5.
Table 5 bushing loss amount/g
| The experiment number | 19 | 20 | 21 | 22 | 23 | 24 |
| Loss amount | 24.1 | 23.4 | 19.7 | 22.9 | 23.2 | 23.8 |
Claims (8)
1. reduce the glass coating of platinum rhodium bushing loss, it is characterized in that, become with Suzhou local soil type by glass ingredient, the part by weight of glass ingredient and Suzhou soil is 9-15:1.
2. glass coating according to claim 1 is characterized in that, the part by weight of glass ingredient and Suzhou soil is 9-11:1.
3. glass coating according to claim 1 is characterized in that, the part by weight of glass ingredient and Suzhou soil is 9,11,13 or 15:1.
4. according to the arbitrary described glass coating of claim 1-3, it is characterized in that the composition of said glass ingredient is: 45～55 parts SiO
2, 35～45 parts Al
2O
3, 6～12 parts Na
2O, CaO are 1～4 part, and MgO is 0.5～3 part, 0.1～0.6 part Li
2O, 0～1 part La
2O
3, be weight part.
5. glass coating according to claim 4 is characterized in that SiO
2Be 47～51 parts, Al
2O
3Be 35～38 parts, Na
2O is 6～10 parts, and CaO is 1.5～3 parts, and MgO is 1～2.5 part, Li
2O is 0.3～0.5 part, La
2O
3It is 0.5～0.8 part.
6. according to the coating process of the arbitrary described glass coating of claim 1-3, it is characterized in that step is following:
(1) colloidal sol preparation: it is native to take by weighing glass ingredient and Suzhou in proportion, mixes to transparently with deionized water, dehydrated alcohol, takes out behind the 32-37 ℃ of water-bath 4-8h, and room temperature preservation is for use;
(2) bushing coating: earlier bushing is cleaned, clean with alcohol, on sol evenning machine, film, the colloidal sol for preparing is dropped in the center that rotates sample, colloidal sol is even film forming under action of centrifugal force; Preferably, pick an amount of colloidal sol wiping sample edges and corners and uncoated place gently with absorbent cotton after the film forming of sample two sides, make it form uniform coating;
(3) sample of will filming is put into resistance furnace and is dried, and accomplishes and films for the first time, repeats above-mentioned steps, and sample is carried out filming the second time.
7. coating process according to claim 6 is characterized in that, step (1) will be stirred to transparent colloidal sol and behind 35 ℃ of water-bath 6h, take out, and room temperature preservation is for use.
8. coating process according to claim 6 is characterized in that dryer is made as: 3 ℃/min in 0～200 ℃ of scope, and 5 ℃/min in 200～1400 ℃ of scopes, temperature is incubated 2 h when rising to 1400 ℃.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105176145A (en) * | 2015-07-14 | 2015-12-23 | 重庆国际复合材料有限公司 | Coating material, composite material, leakage plate support beam and leakage plate support beam preparation method |
| CN107555967A (en) * | 2017-08-02 | 2018-01-09 | 山东玻纤集团股份有限公司 | A kind of glass fiber drain bushing ceramic spraying technique |
| CN108151900A (en) * | 2017-11-16 | 2018-06-12 | 华中科技大学 | A kind of anti-carbon composite coating material of platinum rhodium thermocouple and preparation method thereof |
| CN112474103A (en) * | 2020-11-16 | 2021-03-12 | 无锡英特派金属制品有限公司 | Portable spraying protection device |
| CN114213883A (en) * | 2021-12-31 | 2022-03-22 | 咸阳非金属矿研究设计院有限公司 | Inorganic composite temperature-resistant anticorrosive coating material and preparation method thereof |
| CN115490413A (en) * | 2022-07-28 | 2022-12-20 | 湖南兆湘光电高端装备研究院有限公司 | Method for protecting platinum channel |
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| CN101638294A (en) * | 2009-08-18 | 2010-02-03 | 淄博新力特种纤维科技有限公司 | Coating capable of reducing use loss of platinum bushings and preparation method thereof |
| CN101967313A (en) * | 2010-11-03 | 2011-02-09 | 重庆国际复合材料有限公司 | Protective coating for inhibiting platinum bushing from being oxidized and volatilized, and manufacturing method and application thereof |
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2011
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH06298543A (en) * | 1993-04-09 | 1994-10-25 | Nippon Glass Fiber Co Ltd | Bushing for producing glass fiber and its production |
| CN1875404A (en) * | 2003-10-31 | 2006-12-06 | 柯尼卡美能达精密光学株式会社 | Glass substrate for an information recording medium and information recording medium employing it |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105176145A (en) * | 2015-07-14 | 2015-12-23 | 重庆国际复合材料有限公司 | Coating material, composite material, leakage plate support beam and leakage plate support beam preparation method |
| CN107555967A (en) * | 2017-08-02 | 2018-01-09 | 山东玻纤集团股份有限公司 | A kind of glass fiber drain bushing ceramic spraying technique |
| CN107555967B (en) * | 2017-08-02 | 2023-04-14 | 山东玻纤集团股份有限公司 | Glass fiber wire-drawing bushing plate ceramic spraying process |
| CN108151900A (en) * | 2017-11-16 | 2018-06-12 | 华中科技大学 | A kind of anti-carbon composite coating material of platinum rhodium thermocouple and preparation method thereof |
| CN108151900B (en) * | 2017-11-16 | 2019-08-13 | 华中科技大学 | A kind of anti-carbon composite coating material of platinum rhodium thermocouple and preparation method thereof |
| CN112474103A (en) * | 2020-11-16 | 2021-03-12 | 无锡英特派金属制品有限公司 | Portable spraying protection device |
| CN114213883A (en) * | 2021-12-31 | 2022-03-22 | 咸阳非金属矿研究设计院有限公司 | Inorganic composite temperature-resistant anticorrosive coating material and preparation method thereof |
| CN115490413A (en) * | 2022-07-28 | 2022-12-20 | 湖南兆湘光电高端装备研究院有限公司 | Method for protecting platinum channel |
| CN115490413B (en) * | 2022-07-28 | 2024-01-05 | 湖南兆湘光电高端装备研究院有限公司 | Method for protecting platinum channel |
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