CN114790107A - Preparation of SiO by utilizing polycrystalline silicon cutting waste at low temperature 2 -Si 3 N 4 Method for compounding ceramic - Google Patents
Preparation of SiO by utilizing polycrystalline silicon cutting waste at low temperature 2 -Si 3 N 4 Method for compounding ceramic Download PDFInfo
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Abstract
The invention belongs to the technical field of metallurgical resource recycling, and discloses a method for preparing SiO by using polycrystalline silicon cutting waste at low temperature 2 ‑Si 3 N 4 A method for compounding ceramics. Processing the polycrystalline silicon cutting waste to the standard of laboratory use, mixing the polycrystalline silicon cutting waste with a diluent, uniformly ball-milling, and controlling a nitriding reaction by reasonably selecting a nitriding atmosphere to obtain a nitriding product; crushing and grinding the nitriding product, and adding SiO 2 C, sintering aid, ball milling and mixing, and cold isostatic pressing to prepare a sample before ammoniation; through reasonable selection of ammoniation atmosphere and control of ammoniation reaction, SiO is obtained 2 ‑Si 3 N 4 Composite ceramics. The invention has the advantages that the by-product generation is avoided by controlling the powder composition and ammoniation conditions, and SiO is utilized 2 The volume effect is effectively reduced by the carbothermic reduction reaction of the C and the C, and finally the SiO with uniform components and good performance is obtained 2 ‑Si 3 N 4 The composite ceramic realizes the resource utilization of the photovoltaic industrial chain waste and the economic development of the ceramic industrial chain.
Description
Technical Field
The invention belongs to the technical field of metallurgical resource recycling, and relates to a method for preparing SiO by using polycrystalline silicon cutting waste at low temperature 2 -Si 3 N 4 A method for compounding ceramics.
Background
The polycrystalline silicon cutting waste is one of silicon-based solid waste products brought by the rapid development of the photovoltaic industry, and the annual output is about 200 kilotons. The problems of high difficulty, high cost, high impurity content and the like exist in recovering the simple substance silicon product from the waste, so that a large amount of waste is accumulated, a large amount of land resources are occupied, and resource waste and environmental pollution are caused to a certain extent.
Compared with the method for recycling the simple substance silicon product from the polycrystalline silicon cutting waste, the method directly converts the waste into the high value-added resource such as silicon-based ceramic, omits the necessary step of purifying silicon powder, simplifies the process flow, reduces the raw material cost of the ceramic, and promotes higher additionalProduction of the product. Si 3 N 4 The ceramic is one of the representative high value-added products, and the ceramic has high strength and corrosion resistance, so that the ceramic is widely applied to the mechanical and manufacturing industries, but is limited by high dielectric constant and dielectric loss, and the development of the ceramic in the aerospace industry is limited. SiO 2 2 -Si 3 N 4 The appearance of composite ceramics solves the problem, and the composite ceramics not only have Si 3 N 4 Has high strength and corrosion resistance, and simultaneously has SiO 2 The low dielectric constant and dielectric loss of the material are high-quality materials for preparing aerospace antenna windows and the like. However in the preparation of SiO 2 -Si 3 N 4 In the process of composite ceramic, if silicon powder, silicon dioxide and the like are simply mixed and sintered, by-products such as silicon oxynitride and the like are inevitably generated in the obtained product due to the influence of factors such as oxygen content, particle roughness and the like, so that the dielectric property and the mechanical property of the ceramic product are greatly influenced, and the ceramic product is difficult to apply in practical aspects. Therefore, how to reasonably avoid the generation of silicon oxynitride and other byproducts is to prepare the excellent SiO 2 -Si 3 N 4 The premise of composite ceramic.
Because silicon oxynitride has the characteristic of pyrolysis, the prior art generally adopts the steps of increasing the sintering temperature and synchronously increasing the heat preservation time of a high-temperature interval so as to eliminate byproducts, namely, the byproducts are generated firstly and then are decomposed. However, these control techniques are usually based on high temperature, long time effect and high loss, and the practical economic benefit is not high. If the high-temperature sintering is required to be reduced and the energy consumption is reduced, the conventional control method is to add a certain proportion of sintering aid to form a multi-element eutectic body in the system along with the sintering process, so that the sintering temperature can be reduced to a certain extent. At the same time, however, the formation of part of the multicomponent eutectic also brings about a volume effect of up to 30% or even more, so that the practical yield of the control method is not high. Therefore, there is a need to develop a new method capable of preparing a composite ceramic at a low temperature.
Disclosure of Invention
Si、SiO 2 The mixed powder is difficult to generate SiO in the traditional ceramic preparation process 2 -Si 3 N 4 The composite ceramic is easy to generate silicon oxynitride and other byproducts. Aiming at the problem of easy generation of byproducts, the invention aims to: provides a method for preparing SiO by utilizing polycrystalline silicon cutting waste at low temperature 2 -Si 3 N 4 The method for preparing the composite ceramic effectively avoids the generation of silicon oxynitride and other byproducts by controlling the powder composition and ammoniation conditions and utilizes SiO 2 The carbon thermal reduction reaction with C effectively reduces the volume effect, and finally SiO with uniform components and good performance is obtained 2 -Si 3 N 4 The composite ceramic realizes the resource utilization of the photovoltaic industrial chain waste and the economic development of the ceramic industrial chain.
The invention provides a concept for preparing composite ceramic by nitriding and ammoniating polycrystalline silicon cutting waste to fire ceramic, so that the polycrystalline silicon cutting waste can be used for preparing SiO at low temperature 2 -Si 3 N 4 A method of compounding a ceramic comprising the steps of:
(1) purifying the polycrystalline silicon cutting waste:
drying, crushing, impurity washing, secondary drying, grinding and sieving the polycrystalline silicon cutting waste to obtain powder, namely purified polycrystalline silicon cutting waste, wherein the purity of Si is 2N level;
(2) nitridation treatment of polysilicon cutting waste
Adding a diluent into the purified polysilicon cutting waste obtained in the step (1), performing ball milling and mixing, performing atmosphere nitridation, and performing nitridation reaction to obtain a nitridation product;
the diluent is alpha-Si 3 N 4 Or beta-Si 3 N 4 The adding amount is not more than 20% of the mass of the purified polycrystalline silicon cutting waste.
In the nitridation reaction, the nitridation gas is one of nitrogen or a nitrogen-hydrogen mixed gas, wherein in the nitrogen-hydrogen mixed gas, the volume ratio of the nitrogen to the hydrogen is 75:25-95: 5.
In the nitridation reaction, the nitridation equipment adopts an atmosphere tube furnace with program temperature control, the temperature in the furnace is ensured to rise to 1200-1450 ℃ at the speed of 1-5 ℃/min, and then the constant temperature is kept for 0.5-2.5 h. The temperature raising system is favorable for the nitridation reaction.
The nitriding atmosphere and the diluent are used to promote the progress of the nitriding reaction.
(3)SiO 2 -Si 3 N 4 Ammoniation firing of composite ceramics
Grinding the nitridation product in the step (2) to be less than 300 meshes by using a mortar, and adding a certain proportion of SiO 2 And C, sintering the auxiliary agent, ball-milling until the materials are uniformly mixed, drying the materials, and carrying out cold isostatic pressing to obtain a sample before ammoniation. After ammoniation gas is introduced into the atmosphere tube furnace equipment, the temperature is raised to 1100-1450 ℃ at the speed of 1-5 ℃/min, then the temperature is kept for 1-3h, and the temperature is lowered to room temperature at the speed of 1-5 ℃/min to obtain SiO 2 -Si 3 N 4 Composite ceramics. The heat treatment system can promote the carbon thermal reduction reaction, is beneficial to reducing the volume effect brought by the multicomponent glass phase eutectic, and thus improves the performance of the ceramic sintered body.
The sintering aid is MgO and Al 2 O 3 、Y 2 O 3 The sintering auxiliary agent can reduce the sintering temperature in the ammoniation process; addition of SiO 2 And C, carrying out carbothermic reduction reaction, and reducing the volume effect brought by the ammoniation process.
The SiO 2 And C, the addition amount of the sintering aid does not exceed 100 percent, 20 percent and 20 percent of the mass of the nitriding product respectively.
The ammoniation gas is one of ammonia gas, nitrogen-ammonia mixed gas, hydrogen-ammonia mixed gas and nitrogen-hydrogen-ammonia mixed gas, wherein when the mixed gas is used, the volume ratio of the ammonia gas is controlled to be more than 50%.
The beneficial effects of the invention are as follows:
(1) the main body of the added raw materials is polycrystalline silicon cutting waste. The cost of the ceramic raw material is low, the environmental pollution caused by stacking waste materials is solved, and the formation of an industrial chain of high value-added products is promoted.
(2) The nitriding atmosphere used in the nitriding process is one of nitrogen and nitrogen-hydrogen mixed gas, and the hydrogen can break the natural oxide layer film on the surface of the silicon and effectively promote the nitriding reaction.
(3) NitridingThe diluent added in the process is alpha-Si 3 N 4 Or beta-Si 3 N 4 The total amount is controlled to be not more than 20% of the total weight of the purified polycrystalline silicon cutting waste. The diluent is added to serve as a reaction seed to promote the progress of the nitriding reaction.
(4) The sintering aid added in the ammoniation process is MgO and Al 2 O 3 And Y 2 O 3 One or more of the above-mentioned components, the total amount of which is controlled so as not to exceed 20% of the total weight of the nitrided product. The addition of the sintering aid can generate a multi-element glass phase eutectic, and effectively reduce the sintering temperature of the ceramic sintered body.
(5) SiO is added in the ammoniation process 2 And C, the total amount is controlled according to 100 percent and 20 percent of the total weight of the nitriding product. The general reaction formula of the carbothermic reduction reaction is as follows: 3SiO 2 2 +6C+4NH 3 →Si 3 N 4 +6CO+6H 2 The volume effect brought by the eutectic formed in the sintering process of the sintering aid can be effectively reduced, and the linear shrinkage rate of the ceramic is reduced, so that the mechanical property of the ceramic is improved.
(6) The ammoniation atmosphere used in the ammoniation process is one of ammonia gas, nitrogen-ammonia mixed gas, hydrogen-ammonia mixed gas and nitrogen-hydrogen-ammonia mixed gas. When the mixed gas is used, the ammonia gas accounts for more than 50% of the total gas, and the ammoniated gas can effectively reduce the sintering temperature of the ceramic sintered body and reduce the generation of byproducts.
Drawings
FIG. 1 is a diagram for preparing SiO by using polycrystalline silicon cutting waste at low temperature according to the invention 2 -Si 3 N 4 Process flow diagram of a method of compounding a ceramic.
Fig. 2 shows exemplary XRD results.
Detailed Description
The contents and effects of the present invention will be further described with reference to the following embodiments and data.
Example 1:
taking polycrystalline silicon cutting waste materials of a certain solar cell panel company in a linear cutting stage, wherein the components mainly comprise Si and SiO 2 And a small amount of metal oxide impurities, wherein the purity of Si after purification treatment is 99 percentAbove, a diluent of alpha-Si is added thereto 3 N 4 The adding amount is 20% of the mass of the purified polycrystalline silicon cutting waste; selecting a nitrogen-hydrogen (95:5) mixed gas as a nitriding atmosphere; adding MgO and Y 2 O 3 As a sintering aid, the addition amount is 7 percent of the total mass; nitrogen-ammonia (4: 6) mixed gas is selected as ammoniation atmosphere.
In order to further verify the content and the effect of the invention, the method comprises the following specific process steps:
(1) simultaneously filling the purified polysilicon cutting waste and the diluent into a ball milling tank, uniformly mixing, placing into an alumina crucible, heating to 1400 ℃ in a nitriding atmosphere, preserving heat for 2 hours, and cooling to room temperature along with the furnace to obtain a nitriding product;
(2) crushing and grinding the nitrided product in the step (1), and then adding a sintering aid and SiO 2 And C, after ball milling and mixing are carried out again, the mixture is subjected to cold isostatic pressing and is placed in a graphite crucible, and the components of the sample before ammoniation in the embodiment 1 are shown in the table 1;
table 1 example 1 sample composition before ammoniation
(3) Heating to 1350 ℃ in ammoniation atmosphere, preserving heat for 2.5h, and cooling to room temperature along with the furnace to obtain SiO 2 -Si 3 N 4 Composite ceramics. And (4) carrying out performance test on the obtained composite ceramic.
Example 2:
taking polycrystalline silicon cutting waste materials of a certain solar cell panel company in a linear cutting stage, wherein the components mainly comprise Si and SiO 2 And a small amount of metal oxide impurities, the purity of the purified Si is more than 99 percent, and a diluent beta-Si is added into the purified Si 3 N 4 The adding amount is 10% of the mass of the purified polycrystalline silicon cutting waste; selecting nitrogen-hydrogen (9:1) mixed gas as nitriding atmosphere; adding MgO as a sintering aid, wherein the addition amount is 8 percent of the total mass; nitrogen-hydrogen-ammonia (30:10:60) mixed gas is selected as ammoniation atmosphere.
In order to further verify the content and the effect of the invention, the method comprises the following specific process steps:
(1) simultaneously filling the purified polycrystalline silicon cutting waste and the diluent into a ball milling tank, uniformly mixing, placing the mixture into an alumina crucible, heating to 1300 ℃ in a nitriding atmosphere, preserving heat for 2 hours, and cooling to room temperature along with a furnace to obtain a nitriding product;
(2) crushing and grinding the nitriding product obtained in the step (1), and adding a sintering aid and SiO 2 And C, after ball milling and mixing again, carrying out cold isostatic pressing and placing the mixture into a graphite crucible, wherein the components of the sample before ammoniation in the example 2 are shown in the table 2;
table 2 example 2 sample composition before ammoniation
(3) Heating to 1300 ℃ in ammoniation atmosphere, preserving heat for 1.5h, and cooling to room temperature along with the furnace to obtain SiO 2 -Si 3 N 4 Composite ceramics. And carrying out performance test on the obtained composite ceramic.
Example 3:
taking polycrystalline silicon cutting waste materials of a certain solar cell panel company in a linear cutting stage, wherein the components mainly comprise Si and SiO 2 And a small amount of metal oxide impurities, the purity of the purified Si is more than 99 percent, and a diluent alpha-Si is added into the purified Si 3 N 4 The adding amount is 10% of the mass of the purified polycrystalline silicon cutting waste; selecting high-purity nitrogen as nitriding atmosphere; adding MgO and Al 2 O 3 As a sintering aid, the addition amount is 8 percent of the total mass; ammonia was chosen as the ammoniating atmosphere.
In order to further verify the content and the effect of the invention, the method comprises the following specific process steps:
(1) simultaneously filling the purified polysilicon cutting waste and the diluent into a ball milling tank, uniformly mixing, placing into an alumina crucible, heating to 1400 ℃ in a nitriding atmosphere, preserving heat for 2 hours, and cooling to room temperature along with the furnace to obtain a nitriding product;
(2) crushing and grinding the nitriding product in the step (1)Then adding sintering aid and SiO 2 C, after ball milling and mixing again, carrying out cold isostatic pressing and placing in a graphite crucible, wherein the components of the sample before ammoniation in embodiment 3 are shown in Table 3;
table 3 example 3 sample composition before ammoniation
(3) Heating to 1400 ℃ in ammoniation atmosphere, keeping the temperature for 2 hours, and cooling to room temperature along with the furnace to obtain SiO 2 -Si 3 N 4 Composite ceramics. And carrying out performance test on the obtained composite ceramic.
Example 4:
taking polycrystalline silicon cutting waste materials of a certain solar cell panel company in a linear cutting stage, wherein the components mainly comprise Si and SiO 2 And a small amount of metal oxide impurities, the purity of the purified Si is more than 99%, and a diluent beta-Si is added into the purified Si 3 N 4 The adding amount is 10% of the mass of the purified polycrystalline silicon cutting waste; selecting high-purity nitrogen as nitriding atmosphere; adding Al 2 O 3 And Y 2 O 3 As a sintering aid, the addition amount is 6 percent of the total mass; a mixed gas of hydrogen and ammonia (5: 95) is selected as an ammoniation atmosphere.
In order to further verify the content and the effect of the invention, the method comprises the following specific process steps:
(1) putting the ground and cleaned polycrystalline silicon cutting waste and a diluent into a ball milling tank at the same time, ensuring that the waste and the diluent are uniformly mixed, putting the mixture into an alumina crucible, heating to 1450 ℃ in a nitriding atmosphere, keeping the temperature for 2 hours, and cooling to room temperature along with the furnace to obtain a nitriding product;
(2) crushing and grinding the nitrided product in the step (1), and then adding a sintering aid and SiO 2 And C, after ball milling and mixing again, carrying out cold isostatic pressing and placing the mixture into a graphite crucible, wherein the components of the sample before ammoniation in example 4 are shown in Table 4;
table 4 example 4 sample composition before ammoniation
(3) Heating to 1350 ℃ in ammoniation atmosphere, preserving heat for 2h, and cooling to room temperature along with the furnace to obtain SiO 2 -Si 3 N 4 Composite ceramics. And (4) carrying out performance test on the obtained composite ceramic.
The scanning analysis of the composite ceramics of examples 1, 2, 3 and 4 by X-ray diffraction (XRD) is shown in fig. 2.
The composite ceramics of examples 1, 2, 3 and 4 were subjected to the performance test, and the results are shown in table 5.
TABLE 5 composite ceramic Performance test results
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Relative dielectric constant | 4.8 | 4.0 | 4.2 | 5.1 |
| Linear shrinkage (%) | 5.3％ | 2.62％ | 4.5％ | 1.3％ |
Although the present invention has been described in detail with reference to preferred embodiments, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (10)
1. Preparation of SiO by utilizing polycrystalline silicon cutting waste at low temperature 2 -Si 3 N 4 A method of compounding a ceramic, comprising the steps of:
(1) purifying the polycrystalline silicon cutting waste to obtain purified polycrystalline silicon cutting waste, wherein the purity of Si is 2N grade;
(2) and (3) nitriding the polycrystalline silicon cutting waste:
adding a diluent into the purified polysilicon cutting waste obtained in the step (1), performing ball milling and mixing, performing atmosphere nitridation, and performing nitridation reaction to obtain a nitridation product;
(3)SiO 2 -Si 3 N 4 ammoniation firing of composite ceramics
Grinding the nitriding product in the step (2) by using a mortar, and adding SiO in a certain proportion 2 C, ball-milling the sintering aid until the materials are uniformly mixed, drying the materials, and carrying out cold isostatic pressing to obtain a sample before ammoniation; introducing ammoniation gas into atmosphere tube furnace equipment, heating to the temperature of ammoniation reaction by program, reacting at constant temperature for a period of time, and cooling to room temperature by program after ammoniation reaction is finished to obtain SiO 2 -Si 3 N 4 Composite ceramics.
2. The method of claim 1, wherein in the step (1), the purification treatment process of the polysilicon cutting waste comprises: the polysilicon cutting waste is dried, crushed, washed of impurities, dried again, ground and sieved to obtain powder.
3. The method of claim 1, wherein in step (2), the diluent is α -Si 3 N 4 Or beta-Si 3 N 4 The addition amount is not more than 20 percent of the mass of the purified polysilicon cutting waste.
4. The method of claim 1, wherein in the step (2), the nitriding gas is one of nitrogen gas or a nitrogen-hydrogen mixture gas in the nitriding reaction, wherein the volume ratio of the nitrogen gas to the hydrogen gas in the nitrogen-hydrogen mixture gas is 75:25-95: 5.
5. The method as claimed in claim 1, wherein in the step (2), the nitriding equipment adopts a programmed temperature controlled atmosphere tube furnace to ensure that the temperature in the furnace is raised to 1450 ℃ at a speed of 1-5 ℃/min, and then the temperature is kept constant for 0.5-2.5 h.
6. The method according to claim 1, wherein in the step (3), the nitrided product is ground to 300 mesh or less with a mortar.
7. The method according to claim 1, wherein in the step (3), the sintering aid is MgO or Al 2 O 3 、Y 2 O 3 One or more of them.
8. The method of claim 1, wherein in step (3), the SiO is 2 And C, the addition amount of the sintering aid does not exceed 100 percent, 20 percent and 20 percent of the mass of the nitriding product respectively.
9. The method according to claim 1, wherein in the step (3), the ammoniated gas is one of ammonia gas, a mixture of nitrogen and ammonia, a mixture of hydrogen and ammonia, and a mixture of nitrogen and ammonia, wherein the volume ratio of ammonia gas is controlled to be more than 50% when the mixture is used.
10. The method as claimed in claim 1, wherein in the step (3), the temperature of the ammoniation reaction is 1100 ℃ and 1450 ℃, and the constant temperature is maintained for 1-3 h; the rates of program heating and program cooling are both 1-5 ℃/min.
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