CN1125794C - Process for synthesizing composite ceramic powder - Google Patents

Process for synthesizing composite ceramic powder Download PDF

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CN1125794C
CN1125794C CN 99100590 CN99100590A CN1125794C CN 1125794 C CN1125794 C CN 1125794C CN 99100590 CN99100590 CN 99100590 CN 99100590 A CN99100590 A CN 99100590A CN 1125794 C CN1125794 C CN 1125794C
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slurry
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陈大明
李斌太
杜林虎
周洋
华文君
赵新英
徐荣九
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北京航空材料研究院
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Abstract

本发明涉及一种合成多组元陶瓷复合粉体的新方法。 The present invention relates to a new method for the synthesis of multi-component ceramic composite powder. 本发明通过加入可以形成水凝胶的有机单体和交联剂,在引发剂的作用下,使球磨均匀的水料浆快速原位凝胶化,以保持多组元成分的均匀性。 The present invention may be formed of organic monomers and crosslinkers by adding the hydrogel, under the action of an initiator, so that a homogeneous aqueous slurry of ball milled fast in situ gelling, in order to maintain the uniformity of the multi-component composition. 然后将湿凝胶块脱水、干燥、煅烧,合成所需的陶瓷复合粉体。 The wet gel pieces were dehydrated, dried, calcined ceramic composite powder, required for the synthesis. 本发明比传统的固相反应合成法效率高,合成温度低,合成粉体质量好、易粉碎;而比聚丙烯酰胺液相凝胶法以及化学共沉淀法或溶胶-凝胶法,原料来源方便、成本低、操作简便、适用性强、环境污染小,便于工业化生产。 Synthesis reaction of the present invention with high efficiency, low synthesis temperature, good quality synthetic powder, friable than conventional solid; the ratio of polyacrylamide gel and liquid chemical coprecipitation method or sol - gel method, sources of raw materials convenient, low cost, simple operation, applicability, environmental pollution, ease of industrial production.

Description

陶瓷复合粉体合成方法 Ceramic composite powder synthesis method

本发明属于无机非金属材料领域,涉及到多组元陶瓷复合粉体固相反应合成技术的改进。 The present invention belongs to the field of inorganic material, the improvement relates to multi-component composite ceramic powders solid state reaction techniques.

绝大多数功能陶瓷和功能涂层所使用的粉体原料都是多组元复合粉体,这些粉体的工业化生产通常是采用湿法球磨混合、干燥、压块然后经固相反应法煅烧合成。 The vast majority of functional ceramic raw material powder and functional coatings used are multi-component composite powder, the industrial production of these powders typically by a wet ball mill mixing, drying, and then calcined compact synthesized by solid phase reaction method . 在湿法混磨均匀的料浆脱水干燥过程中,多组元粉粒因比重、悬浮性的不同,容易出现组元沉降,一般需通过压滤、喷雾或冷冻法干燥来减少此过程造成的成分不均匀性,这必然增加设备投资和提高工艺成本。 In the wet grinding uniformly mixed slurry was dried process, multicomponent particles by gravity, the different properties of the suspension, settlement prone component, this process is generally required to reduce caused by pressure filtration, freeze or spray drying method unevenness component, which necessarily increases investment in equipment and process costs increase. 在煅烧合成时,若以自然堆积方式进行,多组元粉粒之间接触不好,效率低且使易浑发成分散失;若压块成型后再煅烧可提高反应效率,但由于压块致密度不均匀容易造成局部烧结结块。 Upon calcination synthesis, if the manner of repose, a bad contact between the multi-component particles, inefficient and prone to make muddy component hair loss; if briquetting after calcination can improve the reaction efficiency, but due to the compact actuator sintering density unevenness is likely to cause localized agglomeration. 总之,传统的固相反应合成法生产复合粉体存在着各组元成分难以混合均匀、合成温度高、粉粒粗大等缺点,而且常常得不到所需的相组成。 In short, the conventional solid state reaction method of producing a composite powder components exist in each component is difficult to uniformly mixed, high temperature synthesis, coarse particles and other shortcomings, and often lack the desired phase composition.

近年来液相制粉法的发展为多组分超细粉体的制备提供了很好的新方法。 A new method provides a good milling method developed in recent years for the preparation of liquid multicomponent Ultrafine Powder. 由于液相中各组分的含量可精确控制,并可以实现分子、原子水平上的均匀混合,得到的粉体具有很好的性能,因而成为目前实验室和工业上较为广泛采用的方法。 Since the content of each component of the liquid phase can be precisely controlled, and can achieve molecular homogeneously mixed on the atomic level, to obtain a powder having good performance, the present method thus become more widely used in laboratories and in industry. 在多组分功能陶瓷粉体的液相制备中,共沉淀法和溶胶-凝胶法较多地被使用。 In the preparation of multi-component functional ceramic powder in a liquid phase, co-precipitation method and sol - gel method to be used more. 共沉淀法原料成本低,易于制备多组分体系粉体,但其聚沉过程和多次的过滤水洗过程相当费时、繁琐。 Low cost of raw materials coprecipitation powder easy to prepare multi-component system, but the coagulation process and the washing process multiple filter time-consuming, tedious. 而且对于多组分复合体系,因溶液中不同金属离子生成沉淀的条件不同,让组成材料的多种离子同时沉淀几乎是不可能的。 But also for multi-component composite system, because different metal ions in solution to form a precipitate of different conditions, so that the ionic composition of the material at the same time precipitation is almost impossible. 同时,不同沉淀物溶解度积不同,水洗过程中可能会发生部分组元的流失,造成成分的不准确,影响合成粉体的性能。 Meanwhile, various different solubility product precipitate, part of the washing process component loss may occur, resulting in inaccurate component, affect the performance of synthetic powders. 溶胶-凝胶法利用胶体粒子良好的分散性以及适当的脱水、干燥工艺,可以得到纳米超微粉体。 Sol - gel method using colloidal particles good dispersibility and a suitable dehydration, the drying process can be obtained nano superfine powder. 但它一般都以价格较贵的金属醇盐为原料,成本高、周期长,而且溶胶凝胶过程的控制也有一定困难,若脱水方法不当时,出现缩聚、结块现象,造成颗粒的硬团聚,因此其工业化生产受到了很大限制。 But it is generally more expensive to metal alkoxide as a raw material, high cost, long cycle, and control the sol-gel process also has certain difficulties, not the time when the dehydration process, polycondensation occurs, agglomeration, resulting in a hard agglomerated particles therefore its industrial production has been greatly limited.

1989年法国A.Douy和P.Odier提出了一种聚丙烯酰胺液相凝胶法合成陶瓷氧化物超细粉体的方法(Mat Res Bull.,Vol.24,pp.11191126,1989,Printed in the USA,Pergamon Press plc.),该法采用水溶性的无机盐(通常为硝酸盐、氯盐等)为原料,溶入含有配体柠檬酸的水溶液中,用氨水调整溶液pH值,同时外加有机单体和交联剂,在一定条件下获得液体凝胶。 1989 French A.Douy and P.Odier proposed method (Mat Res Bull synthetic ceramic oxide ultrafine powder a liquid polyacrylamide gel., Vol.24, pp.11191126,1989, Printed in the USA, Pergamon Press plc.), which method uses a water-soluble inorganic salt (typically a nitrate, chloride, etc.) as a raw material, dissolved in an aqueous solution containing a ligand of citric acid, the pH of the solution is adjusted with aqueous ammonia, applied simultaneously organic monomer and a crosslinking agent, to obtain a liquid gel under certain conditions. 然后脱水、干燥、煅烧合成陶瓷粉体。 Then dehydrated, dried, calcined ceramic powder synthesis. 国内李飞跃[功能材料,1992,Vol.23(3),P.157]、李强等人[首届全国纳米材料应用技术交流会资料汇编,1997,普陀山,P.130]也用此种液相凝胶法制备了多种超细粉体。 China Li Feiyue [Functional Materials, 1992, Vol.23 (3), P.157], Li Qiang, et al. [First National nano-materials technology exchanges data compilation, 1997, Putuo Mountain, P.130] also use this solution phase gels prepared by a variety of ultra-fine powder. 但该工艺须采用水溶性盐为原料,使其应用范围受到一定限制。 However, this process shall be a water soluble salt as a raw material, so that the application range is limited. 同时,配体是按金属离子的每一价结合一分子柠檬酸的比例加入,用量很大,而为保持溶液为中性或弱碱性,还需加入大量氨水。 Meanwhile, the proportion of each ligand is a divalent metal ion binding molecule of citric acid was added, a large amount, while maintaining the solution is neutral or weakly basic, needs a large amount of ammonia added. 这不但大大增加了成本,而且煅烧合成时会分解出大量的腐蚀性有害气体如NH4Cl、HCl、HNO3、Cl2、NO、NO2等,严重损坏炉体、加热体,并造成环境污染,很难应用于工业化生产。 This not only greatly increases the cost, but also decompose upon calcination synthesized large amounts of harmful gases such as corrosive NH4Cl, HCl, HNO3, Cl2, NO, NO2, severe damage to the furnace, the heating body, and cause environmental pollution, is difficult to apply industrial production.

本发明的目的是:提出一种多组元复合粉体合成的新方法——凝胶固相反应合成法,以克服传统固相反应法存在的多组元分散不均带来的问题以及常规液相法存在的洗涤、过滤操作繁琐和成本高等缺点,同时,避免上述液相凝胶法带来的有害腐蚀气体损坏设备和污染环境的问题。 Object of the present invention is to: propose a new method for the synthesis of multi-component composite powder - the gel solid state reaction method, in order to overcome the problem of multi-component dispersion variation of the traditional solid phase reaction method and a conventional brought the presence of a washing liquid, filtering and high cost and complicated operation, while avoiding the above-described liquid-gel method brought the issue of harmful etching gas equipment damage and contamination of the environment.

本发明的技术方案是:一种陶瓷复合粉体合成方法,其特征在于采用下述工艺步骤:1、采用与传统的固相反应合成法基本相同的原材料,其中微量添加元素采用水溶性盐类,将欲合成粉体的原材料按规定配比制备成水料浆进行球磨,球料比为1∶1~5∶1,加水量是原料重量的20~200%,球磨时间为1~10O小时;2、在球磨出料前的0.5~15小时内,向料浆内加入有机单体和交联剂,有机单体是丙烯酰胺或者甲基丙烯酰胺其中之一,交联剂是亚甲基双丙烯酰胺或者多乙二醇二甲基丙烯酸其中之一,有机单体和交联剂的总加入量是原料重量的1~10%,有机单体与交联剂的重量比为3∶1~30∶1;3、将球磨后的料浆置于容器中,加入引发剂,加入量是有机单体重量的0.1~0.5%,搅拌均匀,引发剂是下列物质之一:过硫酸铵或者双偶氮[醚丙烷]盐酸,使用时配制成5 Aspect of the present invention is: a ceramic composite powder synthesis method, characterized by using the following process steps: 1, the reaction using substantially the same phase synthesis of raw materials and conventional solid, wherein additional trace elements, water-soluble salts of , the raw material powder to be synthesized according to a predetermined ratio to prepare an aqueous slurry of ball milled, ball to powder ratio of 1 ~ 5:1, the amount of water is 20 to 200% by weight of the starting material, milling time is 1 ~ 10O h ; 2, 0.5 to 15 hours in a ball mill before the discharge, the organic monomer and a crosslinker, an organic monomer is added into the slurry is an acrylamide or methacrylamide wherein one of the crosslinking agent is methylene bisacrylamide or wherein one of the plurality of ethylene glycol dimethacrylate, the total amount of the organic monomer and the crosslinker is added is 1 to 10% by weight of the starting material, the weight ratio of the organic monomer and the crosslinking agent is 3:1 ~ 30:1; 3, the slurry was ball-milled in a container, add the initiator is added in an amount of 0.1 to 0.5% by weight of organic monomers, stir the initiator is one of the following materials: ammonium persulfate or disazo [ether propane] hydrochloride when formulated using 5 20%的水溶液;4、采用下述甲、乙两种方法其中之一使料浆凝胶化:甲方法:向料浆中加入四甲基乙二胺,加入量为丙烯酰胺重量的0.05~0.3%,搅拌均匀后放置,使其自然凝胶化;乙方法:将料浆加热到40~80℃,使其凝胶化;5、将湿凝胶坯体自容器中取出干燥脱水; 20% aqueous; 4, using one of A, B are two ways in which the slurry gelled the following: Method A: tetramethylethylenediamine was added to the slurry in an amount of 0.05 ~ by weight of acrylamide 0.3%, stirring evenly spaced, so that the natural gelling; method b: the slurry was heated to 40 ~ 80 ℃, gelation; 5, the wet gel body removed from the dehydration vessel;

6、将干燥后的凝胶块置于煅烧炉中加热到规定的合成温度,保温一定时间,获得所需的合成粉块。 6, drying the gel pieces were placed in the calciner is heated to a predetermined synthesis temperature, holding a certain time, the synthetic powder to obtain the desired block.

与传统的固相反应合成法相比,本发明具有许多优点。 Synthesis phase reaction as compared with conventional solid, according to the present invention has many advantages. 首先,本发明通过外加有机单体和交联剂,使料浆发生原位聚合反应形成凝胶体,反应速度可以很快,从而使凝胶体基本保持了混合料浆中各组分的均匀分散性,不容易出现密度梯度。 First, by applying the present invention is an organic monomer and a crosslinker, the slurry polymerization occur in situ gel formation, the reaction rate can be quickly, so that the gel remains substantially uniformly mixed slurry of the components dispersibility, not prone to density gradient. 同时,由于凝胶化是靠有机单体和交联剂发生聚合反应形成高分子网络结构来实现的,与合成粉体原料无关,既可使用水溶性金属盐类,也可使用非水溶性的金属氧化物、金属盐或含有需要组元的酸类,这对于多组分特别是微量元素的均匀分散和低温合成是非常有利的。 Meanwhile, due to the formation of polymer network structure of the gel by an organic polymerization reaction and a crosslinking monomer to achieve, independent of the synthetic material powder, a water-soluble metal salts can also be used water-insoluble metal oxides, metal salts or acids containing the required component, which in particular for multi-component synthesis low and uniform dispersion of trace elements is very advantageous. 另外,凝胶过程非常容易控制,所加入的有机物一般仅为固体原料的3%左右,在600℃即可完全烧除,而且高分子网络结构烧除后所留下的空隙有助于阻碍原料粉粒的烧结粗化,煅烧后得到的粉块疏松易粉碎。 Further, the gel is very easy to control the process, the added organic material is generally only about 3% of the solid feedstock, at 600 deg.] C to burn off completely, and the polymer network structure after the voids left by burning off material helps impede roughening particles sintered powder blocks obtained after calcination loose friable. 而与化学共沉淀法、溶胶-凝胶法及聚丙烯酰胺液相凝胶法相比,本发明原料来源方便、成本低、操作简便、普适性强、环境污染小,适用于工业化大生产。 And chemical co-precipitation method, the sol - gel method, and compared to a liquid phase polyacrylamide gel method, a raw material source of the present invention convenient, low cost, simple, universal, small environmental pollution, is suitable for industrial production.

附图说明 BRIEF DESCRIPTION

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图1是不同工艺合成偏钛酸镁粉体的XRD谱比较。 FIG 1 is a different process TiO3 an XRD spectrum of Comparative magnesium.

下面对本发明进行详细说明。 The present invention will be described in detail. 本发明使用金属氧化物、氢氧化物及不产生或少产生有害气体的盐类及酸类物质为原料,先按一定比例配制成相应的水料浆,加入凝胶用有机单体和交联剂,在一定条件下进行快速原位聚合反应,形成含有多组元固相原料的凝胶块。 The present invention uses metal oxides, hydroxides or less and does not produce harmful gas, salts and acids as raw materials, to the corresponding press certain proportion of the water slurry, and adding organic monomers crosslinked gel with agent, quick-situ polymerization to form a gel block containing the multi-component material in the solid phase under certain conditions. 最后经脱水干燥烧除有机物交通过煅烧发生固相反应得到要求的陶瓷粉体。 Finally by dried organics were fired ceramic powder other traffic calcining a solid phase reaction occurs to give the desired. 本发明工艺的要点为:第一、采用与传统的固相反应合成法基本相同的原材料。 The gist of the present invention is a process: first, the synthesis reaction using the raw materials with substantially the same as the conventional solid. 但对于微量添加元素,应使用水溶性盐类,以便保证混料均匀。 But for additional trace elements, water-soluble salt should be used in order to ensure uniform mixing. 另一方面,在不增加原材料成本的条件下,尽量用不产生或者少产生有害气体的、含有所需金属元素的氢氧化物、草酸盐、碳酸盐、偏钛酸、硼酸物质代替原料中的金属氧化物,以利用其煅烧过程中新生成的氧化物具有较高活性使固相反应合成过程易于进行。 On the other hand, without increasing the cost of the raw material conditions, as far as possible with little or no harmful gases, containing the desired metal element hydroxides, oxalates, carbonates, metatitanic acid, boric acid starting material in place of metal oxide to an oxide during calcination which has generated new high reaction activity of the solid phase synthesis easy. 这些原料分解时仅产生H2O、CO2等气体,而不产生NH4Cl、HCl、HNO3、Cl2、NO、NO2等腐蚀性有害气体,可减少对环境的污染。 Generated when these materials decompose only H2O, CO2 and other gases, without generating NH4Cl, HCl, HNO3, Cl2, NO, NO2 and other harmful corrosive gases, can reduce environmental pollution.

第二、以水为介质,通过充分球磨使各种原料细化并混合均匀。 Second, water as a medium, the various raw materials by ball milling fully refined and mixed well. 可根据磨细和混匀的原则,在1∶1~5∶1之间选取球料比,水的加入量可为料重的20~200%,球磨的时间为1~100小时。 The principles may be added in an amount of ground and mixed in a ball between 1/1 to select 5:1 feed ratio of water may be 20 to 200% by weight of feed, milling time is 1 to 100 hours. 为减少用水量和提高球磨效率,可以加入原料重量0.1~0.5%的、不会引入杂质且在煅烧时可完全烧除的各类分散剂,如聚丙烯酸盐、聚甲基丙烯酸盐、羰酸盐、柠檬酸盐等有机电解质分散剂。 To reduce the milling efficiency and water can be added 0.1 to 0.5% by weight of the raw material, does not introduce impurities and completely burned during calcination can be all kinds of other dispersants, such as polyacrylic acid, polymethacrylic acid salt, a carboxylic acid , citrate and other organic electrolyte dispersant.

第三、于出料前0.5~15小时内加入可以在一定条件下形成水凝胶的有机单体如丙烯酰胺、甲基丙烯酰胺等和交联剂如亚甲基又丙烯酰胺、多乙二醇二甲基丙烯酸等。 A third organic monomer, in the 0.5 to 15 hours before the addition of material may form a hydrogel under certain conditions such as acrylamide, methacrylamide and the crosslinking agent and acrylamide such as methylene, ethylene multiple alcohol dimethacrylate and the like. 两者比例可在3∶1~30∶1之间选取。 Both the ratio can be selected between 3 ~ 30:1. 总加入量为料重的1~10%。 The total weight of the feed was added in an amount of 1 to 10%. 在原料粉体粒度较细、混磨时间小于15小时的情况下,有机单体和交联剂也可以和原料同时加入球磨。 In the fine-grained raw material powder, mixed grinding time of less than 15 hours, the organic monomer and a crosslinking agent may be added simultaneously milling and feed.

第四、将球磨好的带有有机单体和交联剂的料浆倒入容器中,加入引发剂如过硫酸铵、双偶氮[醚丙烷]盐酸等水溶液,搅拌均匀,然后可用下述两种方法中的任一种使料浆凝胶化:甲、加入催化剂四甲基乙二胺,搅拌均匀后放置自然凝胶化。 Fourth, the slurry is milled with a good organic monomer and the crosslinking agent into the container, such as ammonium persulfate initiator was added, an aqueous tetrazo [Propane] such as hydrochloric acid, uniformly stirred, and then the following can be used one of either of two methods the slurry gelled: a catalyst is added tetramethylethylenediamine, stir well laid gelled.

乙、将料浆加热至40~80℃使其凝胶化。 B, the slurry was heated to 40 ~ 80 ℃ gelation. 加热方式可以采用电加热、水浴热、微波加热等。 Heating electric heating can be employed, the hot water bath, microwave heating.

上述引发剂的加入量一般为有机单体重量的0.1~1.0%,催化剂的加入量为有机单体重量的0.05~0.5%。 The amount of the initiator added is generally 0.1 to 1.0% by weight of organic monomers, catalyst is added in an amount of 0.05 to 0.5% by weight of organic monomer.

第五、将湿凝胶坯体自容器中取出干燥脱水,干燥方式可以采用自然干燥、吹风干燥或加热干燥。 Fifth, the wet gel is removed from the container body dehydration, drying may employ natural drying, blow drying or heat drying. 为加快脱水干燥过程,可将凝胶块切成或掰成若干小块。 To accelerate the dehydration process, the gel may be cut into blocks or break it into several pieces.

第六、干燥后的凝胶块置于煅烧炉中加热至规定的合成温度下保温,便获得所需的合成粉块。 Sixth, the dried gel pieces was incubated for calcining furnace heated to a predetermined synthesis temperature, the synthesis will be obtained powder required block. 合成温度和保温时间视不同陶瓷粉体的要求而定。 Synthesis temperature and time depending on the requirements of different ceramic powders may be. 当凝胶块尺寸较大时,为防止有机物急速挥发引起崩裂危险,煅烧时可以采用下述两种方法之一将凝胶块中的有机物烧除:一是将大块的凝胶块破碎成小块后,在220~600℃内缓慢升温,烧除有机物;或者将凝胶块加热到450~600℃,保温0.5~5小时,将有机物烧除。 When the gel block size is larger, in order to prevent cracking caused by volatile organic hazardous rapidly, one of two methods may be employed in the gel block organics burned off during firing: First, the gel mass is broken into chunks after the cubes, slowly warmed within 220 ~ 600 ℃, burning off the organic substance; or the gel mass is heated to 450 ~ 600 ℃, for 0.5 to 5 hours, the organics burn-off. 经上述步骤烧除有机物后,再将炉温提高到规定温度煅烧合成粉体。 After the above steps burn off organics, temperature was subsequently raised to a predetermined temperature calcined powders synthesized.

实施例1,合成偏钛酸镁MgTiO3粉体。 Example 1, magnesium MgTiO3 TiO3 powder.

为了证实本发明的优点,采用A、B、C三种工艺条件进行比较。 In order to demonstrate the advantages of the present invention, the use of A, B, C three processes compared conditions.

A工艺:原材料采用偏钛酸H2TiO3和碱式碳酸镁Mg(OH)2·4MgCO3·6H2O,Mg∶Ti=1∶1,同时加入有机单体丙烯酰胺和交联剂亚甲基双丙烯酰胺,加入量为原材料重量的8%两者比例为20∶1。 Process A: Raw materials used metatitanic H2TiO3 basic magnesium carbonate and Mg (OH) 2 · 4MgCO3 · 6H2O, Mg:Ti = 1:1, simultaneous addition of the organic monomers acrylamide and methylene bis acrylamide crosslinker, both the proportion of 8% by weight was added in an amount of raw material being 20. 并加入去离子水配成料浆后球磨,球∶料=2∶1,水∶料=1.5∶1,球磨时间4h。 After addition of deionized water and formulated into a slurry milling, ball: material = 2, water: material = 1.5, milling time 4h. 出料至玻璃容器中并加入有机单体重量0.5%的引发剂过硫酸铵和0.3%的催化剂四甲基乙二胺,搅拌均匀后放置约10分钟发生凝胶化。 The material was added to a glass container and 0.5% by weight of organic monomer initiator, ammonium persulfate and 0.3% of the catalyst tetramethylethylenediamine, placed gelled about 10 minutes after mixing. 取出湿凝胶块置于80℃烘箱中干燥至恒重,然后放入马弗炉中随炉升温至800℃保温2h,编号A8。 Remove the wet gel piece placed in an oven at 80 ℃ dried to constant weight, and then placed in a muffle furnace with the furnace temperature was raised to 800 ℃ incubated 2h, numbered A8.

B工艺:原材料采用二氧化钛TiO2和碱式碳酸镁Mg(OH)2·4MgCO3·6H2O,Mg∶Ti=1∶1,工艺条件与A工艺完全相同,编号B8。 Process B: Raw materials used in the titanium dioxide TiO2 basic magnesium carbonate and Mg (OH) 2 · 4MgCO3 · 6H2O, Mg:Ti = 1:1, exactly the same process conditions and process A, No. B8.

C工艺:原材料与B工艺相同,不加有机单体和交联剂,球磨条件与A工艺相同。 Process C: the same raw materials and process B, and a crosslinking agent without organic monomer, A milling process conditions are the same. 出料后直接于80℃烘箱中干燥至恒重,然后放入马弗炉中随炉升温至800℃保温2h,即采用传统的固相反应工艺,编号C8。 After discharge directly at 80 ℃ oven dried to constant weight, and then placed in a muffle furnace and heated to 800 deg.] C for 2h with the furnace, i.e. using conventional solid phase reaction process, number C8.

对三种工艺合成的粉体进行X射线衍射分析,其XPD谱见附图1。 Process for the synthesis of the three X-ray powder diffraction analysis, see Figure 1 which XPD spectrum. 可以看出,A8基本为单一的偏钛酸镁结构,而B8和C8没有全部合成。 As can be seen, A8 is a basic magnesium titanate single partial structure, while not all synthetic B8 and C8. 这与A工艺采用偏钛酸为原料,煅烧分解新生成的二氧化钛具有较高的表面活性有关。 This takes metatitanic acid decomposition process A newly generated titanium dioxide having a high surface activity of raw materials, calcination. 而B工艺与C工艺虽然采用的原材料相同,但B8中合成的偏钛酸镁显然多于C8,残留的二氧化钛则少于C8,这说明凝胶固相反应的合成效果优于传统的固相反应法。 The same process and raw materials B and C although the process employed, but synthesized magnesium B8 metatitanic apparent than C8, titanium dioxide is less than the residual C8, which shows the effect of synthetic gel solid-phase reaction is superior to conventional solid reaction.

实施例2,合成W型铁氧体BaZn0.5Co1.5Fe16O27粉体。 2, W-type ferrite Synthesis Example BaZn0.5Co1.5Fe16O27 powder.

原材料采用非水溶性的Fe2O3、BaSO4和水溶性的ZnCl2、CoCl2,其配比为Ba∶Zn∶Co∶Fe=1∶0.5∶1.5∶7.8,同时加入有机单体丙烯酰胺和交联剂亚甲基双丙烯酰胺,加入量为原料重量5%,两者比例为15∶1。 Water-insoluble raw materials used Fe2O3, BaSO4 and water-soluble ZnCl2, CoCl2, which ratio of Ba:Zn:Co:Fe = 1:0.5:1.5:7.8, simultaneous addition of the organic monomers acrylamide and methylene crosslinking agent bisacrylamide, is added in an amount of 5% by weight of the raw material, the ratio of the two 15:1. 加入去离子水配成料浆,用氨水调整料浆pH=8后球磨,球∶料=3∶1,水∶料=0.5∶1,球磨时间5h。 Deionized water was added dubbed slurry with aqueous ammonia to adjust the slurry pH = 8 after milling, ball: material = 3, water: material = 0.5, milling time 5h. 出料后加入有机单体重量0.3%的引发剂过硫酸铵,搅拌均匀后放入玻璃烧杯中,于微波炉中加热,约3Os后凝胶化,取出湿凝胶块,掰成约2cm3的小块置于通风条件下干燥至恒重,然后置于马弗炉随炉升温至1200℃保温2h。 By weight of organic monomer is added after the initiator feed of 0.3% ammonium persulfate, stir placed in a glass beaker, heated in a microwave oven for about 3Os gelled wet gel pieces removed, break it in less than about 2cm3 block is placed under ventilated dried to constant weight and then placed in a muffle furnace with the furnace temperature was raised to 1200 deg.] C incubated 2h. 对合成的铁氧体粉进行X射线衍射结构分析,证明已获得良好的W型平面六角铁氧体结构。 Synthesized ferrite powder X-ray diffraction structural analysis, proved to have good W Hexagonal Ferrites structure. 经与化学共沉淀法同样温度下合成的粉体比较,两者的XRD谱完全相同。 Similarly comparison of the powder chemical coprecipitation at a temperature synthesis, both identical to XRD patterns. 但凝胶固相反应艺从原材料成本、工艺操作等方面显然优于化学共沉淀工艺。 However, gel solid phase reaction arts in terms of raw material costs, the process operation is clearly superior to chemical precipitation processes.

实施例3,合成钛酸钡BaTiO3粉体。 Example 3 Synthesis of barium titanate BaTiO3 powders embodiment.

原材料采用BaCO3和TiO2,其配比为Ba∶Ti=1∶1,同时加入有机单体丙烯酰胺和交联剂亚甲基双丙烯酰胺,加入量为原料重量的3%,两者比例为25∶1。 BaCO3 raw materials used and TiO2, which is a ratio Ba:Ti = 1:1, simultaneous addition of the organic monomers acrylamide and methylene bis acrylamide cross-linking agent added in an amount of 3% by weight of the raw materials, both the ratio of 25 :1. 加入去离子水配成料浆,同时加入料重1%的市售JA-281分散剂(一种丙烯酸和甲基丙烯酸共聚物铵盐水溶液,浓度为30%),并用氨水调整料浆pH值至9后球磨,球∶料=2∶1,水∶料=0.3∶1,球磨时间5h。 Deionized water was added dubbed slurry while adding a dispersant JA-281 commercially available 1% weight of the material (an acrylic and a methacrylic acid copolymer ammonium salt solution, a concentration of 30%), and treated with aqueous ammonia to adjust the pH of slurry after 9 to milling, ball: material = 2, water: material = 0.3, milling time 5h. 出料至玻璃容器中,加入有机单体重量1%的引发剂过硫酸铵和0.5%的催化剂四甲基乙二胺。 Glass container outfeed, the organic monomer is added 1% by weight ammonium persulfate initiator, and 0.5% catalyst tetramethylethylenediamine. 搅拌均匀后放置约5分钟发生凝胶化。 After stirring for about 5 minutes evenly spaced gelled. 取出凝胶块切割成约2cm×2cm×2cm的小方块,吹风脱水干燥至恒重。 The gel was removed small block is cut about 2cm squares of × 2cm × 2cm, hair dried to constant weight. 然后放入马弗炉中加热至600℃保温1h烧除有机物,再进一步升温至1100℃保温2h煅烧合成。 Then placed in a muffle furnace and heated to 600 deg.] C for 1h burn off organics, and then further heated to 2h calcination at 1100 ℃ synthesis. 对合成粉体进行X射线衍射结构分析,证明已完成合成钛酸钡结构,与传统的固相反应合成法在1150℃煅烧合成的效果一样。 Synthetic powder X-ray diffraction structural analysis to demonstrate that the structure and synthesis of barium titanate, the reaction phase synthesis as in the conventional solid calcined 1150 ℃ synthesis results. 但脱水干燥过程比传统的固相反应法节能效果显著,合成温度亦相应降低50℃。 However, the energy saving effect dehydration process than conventional solid phase reaction method significantly lowered correspondingly synthesis temperature 50 ℃.

实施例4,合成多组元压电陶瓷PZT粉体。 Example 4, Synthesis of multi-component PZT piezoelectric ceramic powder.

原材料采用Pb3O4、ZrO2、TiO2、La2O3、Nb2O5、MnO2,其配比为Pb∶Zn∶Ti=1∶0.53∶0.47,外加0.01La、0.012Nb、0.002Mn。 Raw materials used Pb3O4, ZrO2, TiO2, La2O3, Nb2O5, MnO2, which is a ratio Pb:Zn:Ti = 1:0.53:0.47, plus 0.01La, 0.012Nb, 0.002Mn. 同时加入有机单体甲基丙烯酰胺和交联剂亚甲基双丙烯酰胺,加入量为原料重量的2.4%,两者比例为6∶1。 Simultaneous addition of the organic monomers methacrylamide and crosslinker methylene bisacrylamide, is added in an amount of 2.4% by weight of the material, both the ratio of 6:1. 加入去离子水配成料浆,同时加入原料重量0.8%的JA-281分散剂,并用氨水调整料浆pH=9后球磨,球∶料=1.5∶1,水∶料=0.2∶1,球磨时间8h。 Deionized water was added dubbed slurry, while 0.8% of the starting weight JA-281 dispersant, and ammonia used to adjust the slurry pH = 9 after milling, ball: material = 1.5, water: material = 0.2, milling time 8h. 出料至玻璃容器中,加入有机单体重量1%的双氮[醚丙烷]盐酸引发剂,搅拌均匀后将容器浸入60℃热水浴中约5分钟凝胶化。 Glass container outfeed, added 1% by weight of organic monomer dinitrogen [ether propane] hydrochloride initiator, stir uniformly dipped in a hot water bath at 60 deg.] C for about 5 minutes gelled. 取出湿凝胶块掰成约1cm3小块置于坩埚内,先在100℃烘箱中脱水干燥至恒重。 Remove the wet gel pieces break it into small pieces about 1cm3 placed in a crucible, first dried to constant weight in an oven at 100 deg.] C. 然后置于马弗炉中敞盖升温至600℃保温1h烧除有机物,再加盖升温至850℃保温2h煅烧合成。 Then placed in a muffle furnace temperature was raised to open the lid 600 ℃ burn off organics were incubated 1h, then warmed to 850 ℃ stamped calcined for 2h synthesis. 对合成粉体取上、中、下部位三个样品进行X射线衍射结构分析和化学成分分析,表明各部位样品结构和成分完全一致。 Take the synthetic powder, the lower portion of three samples X-ray diffraction structural analysis and chemical analysis, indicated that various parts of the structure and composition of the samples identical. 与传统的固相反应法相比,避免了料浆脱水干燥过程中Pb3O4沉降引起的成分不均匀性,合成粉体质量明显提高。 Compared with conventional solid phase reaction method, the composition of the slurry to avoid dehydration process Pb3O4 subsidence unevenness, significantly improved the quality of synthetic powder.

实施例5,合成多组元热敏陶瓷PTC粉体。 Example 5 Synthesis of multi-component ceramic PTC thermistor powder.

先合成PTC基粉,原材料采用BaCO3、Pb3O4、CaCO3、TiO2和水溶性的YCl3,其配比为Ba∶Pb∶Ca∶Ti∶Y=0.93∶0.03∶0.04∶1.01∶0.0011,加去离子水配成水料浆,同时加入原料重量1%的JA-281分散剂,并用氨水调整料浆pH=9后球磨,球∶料=2∶1,水∶料=0.25∶1。 PTC first synthesized based powder, raw materials used BaCO3, Pb3O4, CaCO3, TiO2, and water-soluble YCl3 in, which ratio of Ba:Pb:Ca:Ti:Y = 0.93:0.03:0.04:1.01:0.0011, with deionized water into water slurry, while adding 1% by weight of the feed JA-281 dispersant, and 9 after milling, ball with aqueous ammonia to adjust the pH slurry =: material = 2, water: material = 0.25. 球磨时间18h后,加入有机单体甲基丙烯酰胺和交联剂聚乙二醇(1000)二甲基丙烯酸,加入量为原料重量的3%,两者比例为3∶1。 After the milling time for 18 h, added an organic monomers and methacrylamide crosslinking agent, polyethylene glycol (1000) dimethacrylate added in an amount of 3% by weight of the raw materials, both the ratio of 3:1. 继续球磨0.5h后出料至塑料容器中,加入有机单体重量0.8%的引发剂双偶氮[醚丙烷]盐酸,搅拌均匀后将容器浸入60℃热水浴中约5分钟凝胶化。 The discharge continues into a plastic container after milling 0.5h, added 0.8% by weight of organic monomer initiator, azo-bis [ether propane] hydrochloride, stir uniformly dipped in a hot water bath at 60 deg.] C for about 5 minutes gelled. 取出湿凝胶块掰成约1cm3小块置于坩埚内,先在100℃烘箱中脱水干燥至恒重。 Remove the wet gel pieces break it into small pieces about 1cm3 placed in a crucible, first dried to constant weight in an oven at 100 deg.] C. 然后置于马弗炉中敞盖升温至600℃保温1h烧除有机物,再加盖升温至1180℃保温2h,合成得到PTC基粉。 Then placed in a muffle furnace temperature was raised to open the lid 600 ℃ burn off organics were incubated 1h, then heated to 1180 ℃ stamped incubated 2h, synthesized PTC base powder.

将基粉粗碎通过0.5mm孔筛,进行二次掺杂。 The base powder coarsely pulverized by a 0.5mm aperture sieve, secondary doping. 二次掺杂原材料采用Sb2O3、MnO2、SiO2、Al2O3、Li2CO3,按规定用量与基粉混合,同时加入有机单体甲基丙烯酰胺和交联剂聚乙二醇(1000)二甲基丙烯酸,加入量为原料重量的3%,两者比例为3∶1。 Secondary raw materials are doped Sb2O3, MnO2, SiO2, Al2O3, Li2CO3, the amount of powder mixed with a predetermined group, while adding organic monomers and methacrylamide crosslinking agent, polyethylene glycol (1000) dimethacrylate, was added in an amount of 3% by weight of the material, both the ratio of 3:1. 加入去离子水配成料浆,同时加入原料重量0.8%的JA-281分散剂,并用氨水调整料浆pH=9后球磨,球∶料=2∶1,水∶料=0.25∶1。 Deionized water was added dubbed slurry, while adding 0.8% by weight of the raw material JA-281 dispersant, and ammonia used to adjust the slurry pH = 9 after milling, ball: material = 2, water: material = 0.25. 球磨时间4h后出料。 After 4h discharge milling time. 用与前述相同的方法凝胶化、脱水干燥,最后在马弗炉中敞盖升温至600℃保温1h烧除有机物,即得到经过掺杂且成分均匀的PTC粉体。 Using the same method as the gelling, dried, and finally warmed to open the lid muffle furnace maintained at 600 deg.] C in 1h burning of organics, and is doped to obtain a uniform powder PTC component.

Claims (3)

1.一种陶瓷复合粉体合成方法,其特征在于采用下述工艺步骤,(1)将欲合成粉体的原材料按规定配比制备成水料浆进行球磨,球料比为1∶1~5∶1,加水量是原料重量的20~200%,球磨时间为1~100小时;(2)在球磨出料前的0.5~15小时内,向料浆内加入有机单体和交联剂,有机单体是丙烯酰胺或者甲基丙烯酰胺其中之一,交联剂是亚甲基双丙烯酰胺或者多乙二醇二甲基丙烯酸其中之一,有机单体和交联剂的总加入量是原料重量的1~10%,有机单体与交联剂的重量比为3∶1~30∶1;(3)将球磨后的料浆置于容器中,加入引发剂,加入量是有机单体重量的0.1~0.5%,搅拌均匀,引发剂是下列物质之一:过硫酸铵或者双偶氮[醚丙烷]盐酸,使用时配制成5%~20%的水溶液;(4)采用下述甲、乙两种方法其中之一使料浆凝胶化:甲方法:向料浆中加入四甲基乙二胺, A ceramic composite powder synthesis method, characterized by using the following process steps, (1) the raw material powder to be synthesized according to a predetermined ratio to prepare an aqueous slurry of ball milled, ball to powder ratio of 1 ~ 5:1, the amount of water is 20 to 200% by weight of the starting material, milling time of 1 to 100 hours; (2) within 0.5 to 15 hours prior to milling the material, and a crosslinking agent was added into the organic monomer slurry , one of the organic monomer is acrylamide or methacrylamide wherein the crosslinking agent is methylene bis acrylamide or acrylate wherein one of polyethylene glycol dimethacrylate, the total amount of organic monomer and crosslinker 1 to 10% by weight of the starting material, the weight ratio of the organic monomer and the crosslinking agent is 3:1 ~ 30:1; (3) milling the slurry placed in a container, add the initiator is added in an amount of organic 0.1 to 0.5% by weight of the monomers, stirring evenly, the initiator is one of the following materials: ammonium persulfate or azo-bis [ether propane] hydrochloride, formulated as a 5% to 20% when using an aqueous solution; (4) the use of said A, b one of two ways in which the slurry gelled: method A: tetramethylethylenediamine was added to the slurry, 入量为丙烯酰胺重量的0.05~0.3%,搅拌均匀后放置,使其自然凝胶化;乙方法:将料浆加热到40~80℃,使其凝胶化;(5)将湿凝胶坯体自容器中取出干燥脱水;(6)将干燥后的凝胶块置于煅烧炉中加热到规定的合成温度,保温一定时间,获得所需的合成粉块。 The amount of from 0.05 to 0.3% by weight of acrylamide, placed Stir, then naturally gelling; Method B: The slurry was heated to 40 ~ 80 ℃, gelation; (5) the wet gel removed from the container body in dehydration; (6) drying the gel pieces were placed in the calciner is heated to a predetermined heating temperature, holding time constant, the synthetic powder to obtain the desired block.
2.根据权利要求1或2所述的陶瓷复合粉体合成方法,其特征在于,欲合成粉体的原材料中含有金属氧化物时,应选择不产生或者很少产生有害气体的、该金属的氢氧化物或者酸或者碳酸盐、草酸盐取代原来的金属氧化物为原料。 The ceramic composite powder synthesis method according to claim 1, wherein, when the raw material powder to be contained in the synthetic metal oxide, should be selected with little or no harmful gases, the metal acid, or hydroxide or carbonate, oxalate replace the original metal oxide material.
3.根据权利要求1或2所述的陶瓷复合粉体合成方法,其特征在于,所说的煅烧凝胶块时,先加热到500~800℃,保温30分钟~4小时,烧除有机物,然后提高到规定温度。 3. The ceramic composite powder synthesis method according to claim 1, wherein, when said calcined gel pieces, first heated to 500 ~ 800 ℃, incubated for 30 minutes to 4 hours, burnt organic matter, then raised to a predetermined temperature.
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CN1321091C (en) * 2004-04-09 2007-06-13 中国航空工业第一集团公司北京航空材料研究院 Solid-phase reacting synthesis of composite ceramic powder non-toxic gel

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CN1314625C (en) * 2005-12-27 2007-05-09 武汉理工大学 Method for synthesizing multi-element, inorganic compound ceramic uniformed powder
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CN102344167A (en) * 2010-08-06 2012-02-08 无锡晶石新型能源有限公司 Raw material mixing method in lithium manganate material wet production technology
CN105418071B (en) * 2015-07-28 2018-01-16 山东合创明业精细陶瓷有限公司 Ultrafine synthesis ZrC-SiC composite powder
CN106518040A (en) * 2016-10-28 2017-03-22 湘潭酷弗聚能科技材料有限公司 Method for synthesizing ceramic composite powder and ceramic composite powder

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