CN112778799B - 一种紫色陶瓷色料粉粒及其制备方法、制得的紫色氧化锆陶瓷 - Google Patents
一种紫色陶瓷色料粉粒及其制备方法、制得的紫色氧化锆陶瓷 Download PDFInfo
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- CN112778799B CN112778799B CN202011644081.0A CN202011644081A CN112778799B CN 112778799 B CN112778799 B CN 112778799B CN 202011644081 A CN202011644081 A CN 202011644081A CN 112778799 B CN112778799 B CN 112778799B
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0009—Pigments for ceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62695—Granulation or pelletising
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62802—Powder coating materials
- C04B35/62805—Oxide ceramics
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
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Abstract
本申请涉及陶瓷材料领域,具体公开了一种紫色陶瓷色料粉粒及其制备方法、制得的紫色氧化锆陶瓷。紫色陶瓷色料粉粒包括显色芯粒和异相包覆层,异相包覆层的含量占紫色陶瓷色料粉粒总质量的0.5‑5wt%;显色芯粒包括尖晶石材料和氧化物,尖晶石材料的含量占紫色陶瓷色料粉粒总质量的55‑91wt%,氧化物的含量占紫色陶瓷色料粉粒的8‑40wt%;该紫色陶瓷色料粉粒的制备包括球磨、干燥、第一次煅烧、粉碎、过筛、异相包裹和第二次煅烧。紫色氧化锆陶瓷由包括氧化锆粉体和紫色陶瓷色料粉粒烧结而成。本申请采用异相包裹方式处理着色成分,提高着色成分的分散均匀性及着色稳定性,呈现较深的紫色,制得的陶瓷产品性能稳定。
Description
技术领域
本申请涉及陶瓷材料领域,更具体地说,它涉及一种紫色陶瓷色料粉粒及其制备方法、制得的紫色氧化锆陶瓷。
背景技术
陶瓷是市场上较为常见的材料,而随着社会的发展,陶瓷的应用范围日渐扩大,在建筑、装饰、家具及日常穿戴配件等领域中都广泛应用,且在上述应用领域中,为满足消费者需求,有采用加入陶瓷色料至陶瓷中以赋予陶瓷产品不同的颜色体现,如紫色陶瓷亦是市面上被广泛追求的有色陶瓷之一,在手机外壳配件、手表表带、手表表壳、日用家具陶瓷件等领域中均有应用。
而对于有色陶瓷,目前有较多采用添加着色料的方式对陶瓷进行颜色改变。相关技术中有添加氧化钕和氧化铝作为着色剂,控制添加量为5-15%,使得陶瓷呈现浅紫色;也有相关技术采用氧化钕、氧化铒、氧化钇、氧化铝在1200-1600℃下烧结制备紫色色料;亦有相关技术采用磷酸钾、磷酸氢二氨、氧化锆、氧化钴混合在1400℃下煅烧制备紫色陶瓷色料。但上述相关技术中采用金属氧化物主要是在陶瓷达到特定紫色的基础上提高陶瓷的耐高温性能,而申请人经过长期研究发现,添加的上述稀土金属氧化物虽然能赋予陶瓷所需的色度值,但是稀土金属氧化物难以控制陶瓷的着色程度,使得批量生产的陶瓷产品色泽不一致;而采用的氧化钴、氧化锰、氧化铁等过渡金属着色剂却具有挥发性,使得在高温烧结情况下容易分解挥发而导致陶瓷的颜色分布不均匀,烧结前后出现色差,且申请人发现此类过渡金属着色剂的掺杂还会降低陶瓷的力学性能。
针对上述中的相关技术,申请人认为对于陶瓷着色稳定的问题仍有继续研究及改善的空间。
发明内容
为了陶瓷着色稳定的问题,本申请提供一种紫色陶瓷色料粉粒及其制备方法、制得的紫色氧化锆陶瓷。
第一方面,本申请提供一种紫色陶瓷色料粉粒,采用如下的技术方案:
一种紫色陶瓷色料粉粒,包括显色芯粒和包覆于所述显色芯粒外壁的异相包覆层,所述异相包覆层的含量占紫色陶瓷色料粉粒总质量的0.5-5wt%;所述显色芯粒包括尖晶石材料和氧化物,尖晶石材料的含量占紫色陶瓷色料粉粒总质量的55-91wt%,氧化物的含量占紫色陶瓷色料粉粒总质量的8-40wt%。
通过采用上述技术方案,在显色芯粒的表面设置异相包覆层,对显色芯粒的着色成分进行了包覆,减少由于着色成分在烧结过程中分解挥发而导致着色不均匀的现象;同时,优选的,异相包覆层为SiO2、ZrO2、ZrSiO4、Al2O3中的一种或者多种的组合,采用含陶瓷成分的材料制成异相包覆层,使得紫色陶瓷色料粉粒应用于制备陶瓷产品时,异相包覆层与陶瓷成分结合性高,异相包覆层亦成为陶瓷的主要成分之一,进而提高了显色芯粒在陶瓷中的分散性和结合性,使得显色芯粒的着色成分分散均匀、着色稳定。
优选的,所述尖晶石材料为钇铝尖晶石、镱铝尖晶石、钐铝尖晶石、镧锆尖晶石、钴铝尖晶石的一种或者多种的组合;所述氧化物为氧化硒、氧化铬、氧化铜、氧化镧、氟化钙、氧化铁中的一种或者多种的组合;所述异相包覆层为SiO2、ZrO2、ZrSiO4、Al2O3中的一种或者多种的组合。
通过采用尖晶石材料与氧化物相复配组成显色芯粒,并通过异相包裹的方式在显色芯粒材料表面形成一层高温保护层,使得显色芯粒对陶瓷材料的着色稳定,且采用的上述尖晶石材料占色料组分的55-91%,其多面体结晶型体能提高陶瓷产品的硬度、抗冲击、耐磨损等性能,并具有优异显色性,能呈现不同的颜色,使与氧化物相复配呈现特定的稳定颜色,而异相包裹层则提高了显色芯粒的耐高温性能,使得色料与陶瓷成分共混烧结时不易分解,使得陶瓷的成色稳定。紫色陶瓷色料粉采用尖晶石材料、氧化物和耐高温异相包覆层材料相复配后可形成稳定的颜色,能够承受住更高的烧结温度,使得显色芯粒中着色成分不易受到高温烧结影响而分解并挥发,使得陶瓷成型后成色稳定,并能提高陶瓷产品的强度性能。另外,在高温烧结的过程中,异相包覆层材料中的元素将会渗入至显色芯粒中,使得异相包覆层以掺杂的形式部分加入至显色芯粒中,使得经过煅烧处理后显色芯粒与异相包覆层的结合性高,提高异相包覆层对显色芯粒的包覆稳定性。因而,采用上述种类的尖晶石材料、氧化物以特定的用量比例复配使用,并经过表面包覆耐高温的异相包覆层后,制得成色稳定的紫色陶瓷色料粉粒,并能与陶瓷制品原料结合稳定,提高紫色陶瓷色料粉粒的着色稳定性。
第二方面,本申请提供一种紫色陶瓷色料粉粒的制备方法,采用如下的技术方案:
一种紫色陶瓷色料粉粒的制备方法,包括如下步骤:
A、球磨及干燥:按照重量百分比,将尖晶石材料、氧化物混合,得到混合粉体,并加入至研磨设备中,然后按照混合粉体与水以重量比为1:1.0-1.5加入纯水,再加入占混合粉体重量的0.1-1.0%的聚丙烯酸铵类分散剂,进行球磨,再烘干处理,得到球磨料;
B、第一次煅烧、粉碎和过筛:将步骤A的球磨料进行第一次煅烧,再将煅烧后的粉体粉碎,过筛后得到显色芯粒;
C、异相包裹和第二次煅烧:按照显色芯粒与水的重量比为1:1-3先将纯水加入至研磨设备中,然后加入占显色芯粒重量的0.1-1.5%的双性表面活性剂,搅拌溶解,再加入显色芯粒,球磨1-2h;最后加入异相包裹材料,继续球磨1-5h后烘干、第二次煅烧,过筛后制得紫色陶瓷色料粉粒。
通过采用上述技术方案,利用异相包裹材料对显色芯粒进行包裹处理,提高显色芯粒中着色成分稳定性,在与陶瓷材料共混制备陶瓷制品的烧结过程中,不易受高温烧结而导致着色成分分散挥发,使制得的陶瓷制品成色均匀、稳定;另一方面,包裹处理后的显色芯粒与陶瓷材料的共混分散稳定,经过上述包裹及煅烧处理后,形成的异相包覆层组成与陶瓷成分相近,且紫色陶瓷色料粉粒烧结过程中异相包覆层以掺杂的形式部分加入至显色芯粒中,利用相近似的成分使得陶瓷制备烧结过程中异相包覆层与陶瓷材料相结合,且异相包覆层作为显色芯粒与陶瓷材料的中介结合介质,提高了显色芯粒与陶瓷材料的结合稳定性,使制得的陶瓷制品成色均匀、着色稳定。
上述制备步骤中,步骤A先利用聚丙烯酸铵类分散剂和水对尖晶石材料、氧化物进行分散,并结合球磨,提高物料的分散性,以制得分散稳定的球磨料;而步骤B中对球磨料进行煅烧处理,使得尖晶石材料、氧化物相结合,以形成稳定的显色芯粒,最后经过粉碎和过400目筛处理;再对至少可过400目筛的显色芯粒进行异相包裹,步骤C利用预先分散溶解的双性表面活性剂水溶液对显色芯粒进行分散,提高显色芯粒的表面活性,然后再将异相包裹材料加入其中并混合,以提高异相包裹材料在显色芯粒的活性表面附着性、接枝稳定性,再经过第二次煅烧处理,异相包裹材料在显色芯粒表面形成稳定的异相包覆层,进而制得分散性好、着色稳定的紫色陶瓷色料粉粒。
其中,步骤A中采用的聚丙烯酸铵类分散剂易溶于水,分散性好,用量少则能起到较好的润湿效果,能促进尖晶石材料、氧化物分散均匀,且研磨起泡性低,使得球磨过程中不易产生气泡,避免由于气泡而导致粉体分散不均。优选的,所述聚丙烯酸铵类分散剂可选用聚丙烯酸铵分散剂5027、聚丙烯酸铵分散剂XA450。
步骤B的第一次煅烧处理具体是将步骤A烘干后的球磨料置于氧化铝匣钵内,再置于烧结炉中进行煅烧;而第一次煅烧过程中,聚丙烯酸铵类分散剂在高温下分解、除去,制得的显色芯粒中不含有聚丙烯酸铵类分散剂成分,或者可能有极少量残余,其残余量在显色芯粒成分中可忽略不计。
同理步骤C的第二次煅烧处理,具体是将烘干后的显色芯粒、异相包裹材料共混料置于氧化铝匣钵内,再置于烧结炉中进行煅烧;而第二次煅烧过程中,双性表面活性剂在高温下分解、除去,制得的紫色陶瓷色料粉粒中不含有双性表面活性剂,或者可能有极少量残余,其残余量在紫色陶瓷色料粉粒成分中可忽略不计。
本申请中,在步骤A混料球磨前,还包括有材料预处理:将尖晶石材料、氧化物进行预煅烧除杂和研磨处理,利用预煅烧处理除去对尖晶石材料、氧化物中的易挥发物(如尖晶石材料、氧化物在储存过程中粘附的油脂等成分,可在高温预煅烧过程中分解、除去),并且降低尖晶石材料、氧化物表面活性,降低表面活性可以降低球磨过程中的团聚,增强球磨过程的粉体分散均匀性,其中预煅烧的温度为500-1150℃,预煅烧时间为0.5-2h。而研磨处理为将原料研磨至粒度D50在0.1-1.0μm,以使原材料在球磨过程中共混均匀,避免原材料的颗粒粒度不均而导致显色芯粒成型不均。
优选的,所述步骤A中,加入聚丙烯酸铵类分散剂后球磨的转速为150-450rpm,球磨时间为1-8h;球磨后烘干的温度为100-250℃,烘干时间为5-15h。
通过控制球磨的转速和球磨时间,使得混合粉体分散均匀,控制烘干温度和时间以除去体系中的水分,进而再进行第一次煅烧处理,避免球磨料中的水分过多而降低了煅烧过程中物料间结合性,或避免球磨料中的水分过多而导致物料煅烧结块、难于粉碎的情况。
其中,步骤A的球磨处理,采用直径的锆球,配合砂磨机进行球磨,且优选采用直径的锆球,并控制锆球添加体积占研磨腔体积的40-70%,确保砂磨机的研磨分散效率,保证对混合粉体进行充分的共混球磨,提高混合粉体的分散性。
优选的,所述步骤B中,第一次煅烧的温度为1000-1400℃,保温时间为1-8h;粉碎至显色芯粒至少可过400目筛。
通过控制第一次煅烧的温度及保温时间,能使尖晶石材料、氧化物分在高温煅烧下结合稳定,形成晶相结构稳定的煅烧物;对煅烧物进行粉碎,并过筛得到显色芯粒,控制其过筛目数,以使得特定目数的显色芯粒具有大的比表面积,能均匀分散于表面活性剂水溶液中,提高异相包裹材料与显色芯粒的分散性及结合稳定性,使制得的陶瓷色料具有优良的分散性,并进一步促进紫色陶瓷色料粉粒在钇稳定氧化锆陶瓷材料中促进组成的分散均匀性。
优选的,所述步骤C中,所述双性表面活性剂为卵磷脂。
通过采用卵磷脂,能改变显色芯粒离子表面电荷种类,起到分散、润湿的作用,促使异相包裹材料在显色芯粒表面附着,进而使得后续第二次煅烧时在显色芯粒表面形成稳定的异相包覆层。
优选的,异相包裹材料为硝化物、氯化物和有机硅中的一种或者多种的组合,所述硝化物为Zr(NO3)4,所述氯化物为AlCl3,所述有机硅为氨基硅烷。
本申请采用的上述异相包裹材料,在表面活性剂水溶液中Zr(NO3)4溶解生成Zr4+,AlCl3溶解生成Al3+,氨基硅烷水解产生硅醇,Zr4+、Al3+易于通过双性表面活性剂附着于显色芯粒表面,硅醇能够与双性表面活性剂的羟基结合而均匀附着于显色芯粒的表面,异相包裹材料在水和表面活性剂的分散作用后,吸附包裹于显色芯粒的表面,然后再经过高温煅烧后形成SiO2、ZrO2、Al2O3、ZrSiO4等材料,形成稳定的异相包裹层。
优选的,所述步骤C中,加入纯水、双性表面活性剂和显色芯粒后在球磨转速为600-1500rpm的条件下球磨1-2h;通过控制球磨转速和时间,使得显色芯粒与双性表面活性剂水溶液充分结合,对显色芯粒起到表面润湿作用,提高后续异相包裹材料与显色芯粒的分散均匀性。然后加入异相包裹材料后在球磨转速为900-3600rpm的继续球磨1-5h,使得异相包裹材料在表面活性剂水溶液中分散均匀,并通过双性表面活性剂吸附于显色芯粒表面,使得经过第二次煅烧后,显色芯粒表面形成稳定的异相包覆层。
优选的,所述步骤C中,加入异相包裹材料并球磨后在温度为100-250℃条件下烘干 4-12h,使得水成分去除,便于异相包裹材料及显色芯粒经过第二次煅烧后制得陶瓷色料;第二次煅烧的温度为500-800℃,第二次煅烧的时间为1-3h,通过控制第二次煅烧的温度和时间,能使异相包裹材料与显色芯粒稳定结合,经煅烧后在表层形成稳定的异相包覆层。
优选的,所述步骤C中,控制第二次煅烧后过筛的目数为至少可过400目筛,则为紫色陶瓷色料粉粒,能保证成型的紫色陶瓷色料粉粒细度较小,分散性好,促进紫色陶瓷色料粉粒均匀分散于陶瓷粉体中进一步制备有色陶瓷。
第三方面,本申请提供一种紫色氧化锆陶瓷,采用如下的技术方案:
一种紫色氧化锆陶瓷,由包括氧化锆粉体和紫色陶瓷色料粉粒烧结而成,所述氧化锆粉体占紫色氧化锆陶瓷质量的80-95%,紫色陶瓷色料粉粒占紫色氧化锆陶瓷质量的5-20%;所述紫色陶瓷色料粉粒为上述的紫色陶瓷色料粉粒,所述氧化锆粉体为含有0-20mol%Al2O3、1- 15mol%Y2O3的钇稳定氧化锆粉体。
本申请制得的紫色陶瓷色料粉粒可直接与氧化锆粉体混合,经过注塑、脱脂、排胶、烧结等步骤后形成稳定的紫色氧化锆陶瓷,且控制紫色陶瓷色料粉粒的用量,能与氧化锆粉体共混分散均匀,并使制得的紫色氧化锆陶瓷呈现特定的深紫色。而采用钇稳定氧化锆粉体,含有氧化钇,能减少在高温烧结制备氧化锆陶瓷过程中发生相变而引起强度退化现象,并控制钇稳定氧化锆粉体中的氧化钇摩尔百分浓度和氧化铝摩尔百分浓度,能使制得的紫色氧化锆陶瓷具有良好的强度、硬度、韧性等性能。
第四方面,本申请提供一种紫色氧化锆陶瓷的制备方法,采用如下的技术方案:
一种紫色氧化锆陶瓷的制备方法,包括如下步骤:
步骤(1):将氧化锆粉体和紫色陶瓷色料粉粒混合,得到混合陶瓷料,然后将混合陶瓷料与水按照重量比为1:1.0-1.7混合,并加入占混合陶瓷料重量的0.1-1.0%的聚丙烯酸铵类分散剂,在转速为900-3600rpm的条件下球磨1-8h,然后进行喷雾干燥处理,得到干燥陶瓷粒;步骤(2):往步骤(1)得到的干燥陶瓷粒添加助剂,然后混炼熔化、密炼,制得密炼料;步骤(3):将步骤(2)制得的密炼料依次进行注塑、脱脂、排胶、烧结,除去聚丙烯酸铵类分散剂及助剂成分,制得紫色氧化锆陶瓷。
通过采用上述技术方案,本申请制得的紫色陶瓷色料粉粒可直接与含有0-20mol% Al2O3、1-15mol%Y2O3的钇稳定氧化锆粉体混合,且分散均匀,并结合陶瓷的助剂制备稳定结构的紫色氧化锆陶瓷,能应用于陶瓷劈刀、手表陶瓷表壳、手机陶瓷背盖等领域中,且制备的步骤操作简便,易于控制,可适用于大规模生产。其中,步骤(1)利用聚丙烯酸铵类分散剂和水将紫色陶瓷色料粉粒与氧化锆粉体进行分散,并结合球磨,提高物料的分散性,得到浆料状态的球磨料,然后将球磨料进行喷雾干燥,得到干粒状态的干燥陶瓷粒;步骤 (2)将干燥陶瓷粒与添加助剂混合混炼熔化、密炼,使得干燥陶瓷粒与陶瓷助剂相容均匀,制得待成型的密炼料。
而制得的密炼料在注塑过程中,加入至注塑机中,受热再次融化为可蠕动的浆料状态,再而注塑至特殊形状的模具内成型,则得到的具有特定形状的陶瓷生坯,其中注塑模具可根据所需的陶瓷制品进行选择,如制备手表陶瓷表壳则采用表壳的注塑模具,制备手机陶瓷背盖则采用背盖的注塑模具、制备陶瓷劈刀则采用劈刀成型注塑模具。
其后,将注塑成型的陶瓷生坯通过加热脱脂,在坯体烧成前将其中的有机物排除干净,以保证产品的形状、尺寸和质量的要求,所排出的有机物包括聚丙烯酸铵类分散剂及所添加粘接剂、增塑剂;由于助剂成分中粘接剂组分受热软化,坯体在中立和热应力的作用下易产生粘性流动变形,使得粘接剂在脱脂过程中可能未排除干净,因而排胶主要是将脱脂过程中未排除干净的粘接剂组分挥发或分解,从而从坯体中脱出,减少由于粘接剂组分而使得陶瓷产品容易变形,使紫色氧化锆陶瓷具有较佳的强度。
最后通过烧结处理,紫色陶瓷色料粉粒的异相包覆层由于含有ZrO2、SiO2、Al2O3等成分,且色料与钇稳定氧化锆粉体在助剂和球磨的作用下形成均匀的混合物,通过烧结后,紫色陶瓷色料粉粒均匀的分布于钇稳定氧化锆陶瓷内部,使其能稳定地着色于氧化锆陶瓷,且异相包覆层的包覆保护使得显色芯粒的着色成分在高温烧结过程中不易分解而挥发,解决了着色稳定性的问题,使得烧结后的陶瓷颜色稳定,没有色差。且显色芯粒的尖晶石材料在烧结后提高了紫色陶氧化锆陶瓷的硬度、抗冲击、耐磨损、耐高温性能,同时解决了过渡金属氧化物导致陶瓷强度性能下降的问题。
本申请中,步骤(1)中采用的聚丙烯酸铵类分散剂易溶于水,分散性好,用量少则能起到较好的润湿效果,能促进紫色陶瓷色料粉粒与氧化锆粉体的分散均匀性,且聚丙烯酸铵类分散剂的研磨起泡性低,使得球磨过程中不易产生气泡,避免由于气泡而导致粉体分散不均。优选的,所述聚丙烯酸铵类分散剂可选用聚丙烯酸铵分散剂5027、聚丙烯酸铵分散剂XA450。
另外,步骤(1)中控制球磨的转速和球磨时间,使得混合陶瓷料分散均匀,以形成浆料状态的球磨料,再进行喷雾干燥除水,使得包含氧化锆粉体和紫色陶瓷色料粉粒的干燥陶瓷粒后续易于与助剂混合。其中,球磨处理采用直径的锆球,配合砂磨机进行球磨,且优选采用直径的锆球,并控制锆球添加体积占研磨腔体积的40-70%,确保砂磨机的研磨分散效率,保证对混合陶瓷料进行充分的共混球磨,提高紫色陶瓷色料粉粒与氧化锆粉体的分散性。
优选的,所述步骤(1)中,喷雾干燥的进风温度为180-260℃,出风温度为100- 130℃;通过控制喷雾干燥的进风温度和出风温度,使得体系中的水分充分去除,形成干粒状态的陶瓷料,进而再进行混炼熔化和密炼,提高干燥陶瓷料与助剂的混合性,避免球磨料中的水分过多导致混炼和密炼过程中物料结团,进而影响混炼、密炼的分散性。
优选的,所述步骤(2)中,混炼熔化过程中添加的助剂包括粘接剂、增塑剂、润滑剂和骨架剂,混炼熔化的温度为50-150℃,混炼熔化的时间为0.5-8h,密炼的时间为1-8h;通过控制混炼熔化的温度和时间,以及密炼的时间,能使得紫色陶瓷色料粉粒、氧化锆粉体与助剂分散均匀,在后续烧结过程中结合稳定。
而通过采用粘接剂,将紫色陶瓷色料粉粒与氧化锆粉体粘合稳定,使物料间紧密接触,并使在加热的情况下,物料具有流动性,使其能在模具中成型特定形状的产品,使其高温烧结后形成形状、性能稳定的陶瓷制品。所述粘接剂添加量为干燥陶瓷粒(氧化锆粉体与紫色陶瓷色料粉粒)总质量的2-10%,粘接剂可以为石蜡、聚乙烯、聚苯乙烯、聚丙烯、环氧树脂、酚醛树脂、聚苯乙烯、乙烯-醋酸乙烯脂共聚物、乙酸丙烯酸乙酯共聚物中的一种或者多种的组合,上述的粘接剂性能稳定,在脱脂及排胶处理中易排出,能够保证紫色氧化锆陶瓷高温烧结成型过程中不产生大的形变,并能将模具成型形状保留至最终紫色陶瓷制品。
通过采用增塑剂,能提高陶瓷材料的可塑性,改善陶瓷材料的强度,提高紫色陶瓷色料粉粒与氧化锆粉体的结合性能,进而提高着色成分的着色稳定性,改善烧结前后的色差问题。所述增塑剂的添加量为干燥陶瓷粒(氧化锆粉体与紫色陶瓷色料粉粒)总质量的2-7%,采用的增塑剂可以为邻苯二甲酸二丁酯、邻苯二甲酸二乙酯、邻苯二甲酸二辛酯、邻苯二甲酸二异辛酸、微晶石蜡、钛酸酯偶联剂、硅烷偶联剂中的至少一种。上述的增塑剂在脱脂过程中容易排出,而可能未完全排出的增塑剂在高温烧结过程中亦分解排出,在紫色陶瓷制品中不含有增塑剂成分,或是存在极小量残余,该残余量在紫色陶瓷制品中亦可忽略不计,不影响氧化锆粉体与紫色陶瓷色料粉粒的成分占比。
通过采用润滑剂,可润湿紫色陶瓷色料粉粒与氧化锆粉体表面,提高粉料的流动性,并能使陶瓷材料具有自润滑性,注塑后坯体易脱模,增加坯体表面光滑性。所述润滑剂的添加量为干燥陶瓷粒(氧化锆粉体与紫色陶瓷色料粉粒)总质量的0.5-5%,采用的润滑剂可以为油酸、硬脂酸、硬脂酸锌、硬脂酸钙中的一种。
而通过采用骨架剂,可防止脱脂过程中由于粘合剂脱除,生坯崩塌,骨架剂主要做为脱脂排胶过程中维持生坯骨架、使之不产生崩塌的作用。所述骨架剂的添加量为干燥陶瓷粒(氧化锆粉体与紫色陶瓷色料粉粒)总质量的1-5%,采用的骨架剂可以为高密度聚乙烯、中密度聚乙烯、低密度聚乙烯、聚丙烯、聚甲醛。
上述的润滑剂和骨架剂在脱脂、排胶及烧结过程中并未排出,在烧结过程中,部分润滑剂和骨架剂受热分解而除去,但仍有残余部分的润滑剂,以保证烧结后紫色陶瓷制品易于脱模,并仍有残余部分的骨架剂,以保证烧结过程成型稳定、不易崩塌,在脱模后,紫色陶瓷制品仍有余温,润滑剂和骨架剂在余温下逐渐分解除去,使得紫色陶瓷制品降温冷却后,紫色陶瓷制品中基本不含有润滑剂和骨架剂,或是含有极小量残余,而该极小的残余量相对于氧化锆粉体与紫色陶瓷色料粉粒的用量而言可忽略不计。
优选的,所述步骤(3)中,注塑过程为当密炼料受热熔融呈胶状浆料后进行注塑,溶胶温度为50-200℃,射胶时间为1-15s,模具温度为50-250℃,注塑速度为3-20cm3/s,注塑压力为20-200T,冷却时间为1-12s;通过控制密炼料的溶胶温度,使得密炼料在注塑过程中于特定溶胶温度下受热,再次熔融,并形成胶状浆料状态,该胶状浆料状态的密炼料注塑至模具中成型,而通过控制注塑过程中的射胶时间、模具的温度、注塑速度、注塑压力以及注塑成型后的冷却时间,使陶瓷材料在特定的温度、压力和时间内形成稳定而牢固的设计结构,制得性能稳定的紫色氧化锆陶瓷生坯。
所述步骤(3)中,脱脂的温度为300-450℃,脱脂时间为12-24h;排胶的温度为400-600℃,排胶时间为4-12h;烧结处理是在温度为1350-1550℃的条件下保温2-6h。
通过控制脱脂的温度和时间,以将注塑成型后的陶瓷生坯中的有机物(聚丙烯酸铵类分散剂、粘接剂、增塑剂)排除,若脱脂温度过高或脱脂时间过长,则容易使得紫色氧化锆陶瓷产品出现开裂等问题;若脱脂温度过低或脱脂时间过短,有机物可能由于没有排除干净而导致紫色氧化锆陶瓷产品容易出现变形、夹杂等问题。其中,脱脂可采用热脱脂或酸脱脂的常规技术手段。
而通过控制排胶的温度和时间,以将粘接剂组分挥发或分解而从坯体中脱出,若排胶温度过低或排胶时间过短,则粘接剂组分可能未排出干净,使得紫色氧化锆陶瓷产品容易出现积碳而导致产品内部具有较多的孔洞,降低了产品的强度,且外观观感差;若排胶温度过高或排胶时间过长,则容易出现粘接剂成分排出的同时骨架剂也一并排出,导致转炉过程中,由于排胶后的坯体强度太差而碎裂。
通过控制烧结的温度和时间,能使紫色陶瓷色料粉粒的异相包覆层与氧化锆粉体在高温烧结过程中形成牢固的晶相结合,进而提高紫色陶瓷色料粉粒与氧化锆粉体的结合性,使得色料着色稳定,且异相包覆层的包覆作用以及耐高温作用,使得着色成分(尖晶石材料、氧化物)在高温烧结过程中不易受高温分解而挥发,改善烧结前后陶瓷材料出现色差的问题;且紫色陶瓷色料粉粒与氧化锆粉体稳定结合后,尖晶石材料在陶瓷体系中起到增加陶瓷强度、硬度、韧性的作用。
本申请的紫色氧化锆陶瓷制备步骤中,在烧结成型制得紫色氧化锆陶瓷后,还包括 CNC处理及抛光处理,利用CNC对成型产品进行披锋,去除产品外形余量,然后利用滚抛的方式对产品的内外表面抛光4-12h,制得紫色氧化锆陶瓷成品。
综上所述,本申请具有以下有益效果:
1、本申请的紫色陶瓷色料粉粒采用尖晶石材料、氧化物经过分散及煅烧处理后形成显色芯粒,再在显色芯粒表面设置异相包覆层,对显色芯粒的着色成分进行包裹保护,使得陶瓷色料粉粒在高温烧结过程中不易高温分解而导致着色成分挥发,进而使得陶瓷色料粉粒着色稳定,烧结后陶瓷产品表面颜色均匀一致;且显色芯粒中的尖晶石材料其能促进氧化锆陶瓷晶格之间的结合,进而提高陶瓷产品的硬度、抗冲击、耐磨损等性能。
2、本申请紫色陶瓷色料粉粒的制备步骤,先将尖晶石材料、氧化物共混后煅烧,形成稳定的显色芯粒,再将显色芯粒、异相包裹材料共混煅烧,在显色芯粒表面形成稳定的异相包覆层,利用异相包覆层提高紫色陶瓷色料粉粒的显色芯粒在高温烧结过程中的稳定性,并与陶瓷材料结合稳定,进而提高显色芯粒中着色成分对陶瓷的着色稳定性,在异相包覆层的包裹保护作用下,解决着色成分在烧结过程中高温分解并挥发而导致着色不稳定、烧结前后色差大的问题。
3、本申请制得的紫色陶瓷色料粉粒可直接与氧化锆陶瓷材料共混,然后结合粘接剂、润湿剂、增塑剂等助剂共混、密炼、注塑、烧结,制得的紫色氧化锆陶瓷具有较高的硬度、强度、韧性等性能,且着色稳定,烧结得到的陶瓷材料色差小,稳定性高,且紫色氧化锆陶瓷可用于进一步加工制备陶瓷劈刀、手表陶瓷表壳、手机陶瓷背盖等产品,应用广泛。
4、本申请制备紫色氧化锆陶瓷的步骤操作简单,过程易于控制,通过球磨共混能使氧化锆粉体和紫色陶瓷色料粉粒共混均匀,再加入其它陶瓷助剂以制备性能稳定的紫色氧化锆陶瓷,可适用于大规模生产。
具体实施方式
以下结合制备例、实施例、对比例对本申请作进一步详细说明。
表1原料厂家型号
项目 | 型号 | 厂家 |
钇稳定氧化锆粉体 | VK-R30Y3或VK-R30Y5 | 杭州智钛净化科技有限公司 |
钇铝尖晶石 | NN-Y-220 | 广州纳诺化学技术有限公司 |
镱铝尖晶石 | 99.9% | 江西安怡新材料科技有限公司 |
钐铝尖晶石 | 99.9% | 江西安怡新材料科技有限公司 |
镧锆尖晶石 | 99.9% | 江西安怡新材料科技有限公司 |
钴铝尖晶石 | NL411 | 湖南诺立新材料有限公司 |
聚丙烯酸铵分散剂5027 | SN5027 | 广州市汇翔化工有限公司 |
聚丙烯酸铵分散剂XA450 | XA450 | 上海中基行化工有限公司 |
环氧树脂 | 6101E44环氧树脂 | 河南汇能树脂有限公司 |
酚醛树脂 | 2123 | 济南大晖化工科技有限公司 |
乙烯-醋酸乙烯脂共聚物 | 货号:250 | 东莞市樟木头梓亿塑胶经营部 |
石蜡 | 58#精炼石蜡 | 郑州旭鑫化工有限公司 |
聚苯乙烯 | RTP | 东莞市卡达尔塑胶原料有限公司 |
油酸 | 植物油酸 | 济南荣信精细化工有限公司 |
高密度聚乙烯 | PH162 | 韩国LG化学 |
中密度聚乙烯 | DX800 | 韩国SK |
低密度聚乙烯 | FN50100 | 美国RTP |
聚丙烯 | GP3156F | 韩国LG |
聚甲醛 | W5320-003 | 德国巴斯夫 |
其中,所述镱铝尖晶石是江西安怡新材料科技有限公司销售的锆酸镱的晶型结构,所述钐铝尖晶石是江西安怡新材料科技有限公司销售的铝酸钐的晶型结构,所述镧锆尖晶石是江西安怡新材料科技有限公司销售的锆酸镧的晶型结构。
制备例
制备例1
一种紫色陶瓷色料粉粒,包括显色芯粒和包覆于显色芯粒外壁的SiO2异相包覆层,SiO2异相包覆层的含量占紫色陶瓷色料粉粒总质量的5%;显色芯粒包括钇铝尖晶石和氧化硒,钇铝尖晶石的含量占紫色陶瓷色料粉粒总质量的55%,氧化硒的含量占紫色陶瓷色料粉粒总质量的40%。
所述紫色陶瓷色料粉粒的制备方法,包括如下步骤:
A、球磨及干燥:按照重量百分比,将钇铝尖晶石、氧化硒混合,得到混合粉体,并加入至研磨设备的料筒中,然后按照混合粉体与水的重量比为1:1.0加入纯水,再加入占混合粉体重量0.1%的聚丙烯酸铵分散剂5027,再加入直径的锆球,球磨锆球添加体积占研磨料筒的研磨腔体积的40%,再将料筒置于砂磨机中,在转速为900rpm的条件下球磨6h,再在温度为100℃的条件下烘干15h,得到球磨料;
B、第一次煅烧、粉碎和过筛:将步骤A的球磨料在温度为1000℃的条件下煅烧8h,除去聚丙烯酸铵类分散剂成分,再将煅烧后的粉体粉碎,过400目筛,将至少400目筛的粉粒收集,得到得到显色芯粒;
C、异相包裹和第二次煅烧:按照显色芯粒与水的重量比为1:1先将纯水加入至研磨设备的料筒中,然后加入占显色芯粒重量0.1%的卵磷脂,搅拌溶解,再加入显色芯粒,在转速为 600rpm的条件下球磨2h;再加入异相包裹材料,在转速为900rpm的条件下继续球磨5h,最后在温度为100℃添加下烘干12h,再在温度为500℃的条件下煅烧3h,过400目筛,将至少400目筛的粉粒收集,得到紫色陶瓷色料粉粒。
制备例2-5
制备例2-5与上述制备例1的区别在于物料种类及用量的差异,以及工艺条件的差异,具体参见下表2;
表2制备例1-5的物料种类、物料用量及工艺条件
制备对比例6
本制备例与上述制备例3的区别在于:
采用等量的氧化铬替代钐铝尖晶石。
制备对比例7
本制备例与上述制备例3的区别在于:
采用等量的钐铝尖晶石替代氧化铬。
制备对比例8
本制备例与上述制备例3的区别在于:
该紫色陶瓷色料粉粒为未经异相包裹处理的显色芯粒;该紫色陶瓷色料粉粒的具体制备方法中,在步骤B煅烧后粉碎、过筛,制得显色芯粒后不经过步骤C的异相包裹及煅烧处理,得到未经异相包裹处理的显色芯粒;则将该显色芯粒直接应用于陶瓷材料的制备。
制备对比例9
本制备例与上述制备例3的区别在于:
紫色陶瓷色料粉粒的制备方法中,步骤C异相包裹后不经煅烧处理,而采用喷雾干燥方式制得紫色陶瓷色料粉粒;
具体步骤为:按照显色芯粒与水的重量比为1:2先将纯水加入至研磨设备的料筒中,然后加入占显色芯粒重量0.8%的卵磷脂,搅拌溶解,再加入显色芯粒,在转速为1000rpm的条件下球磨1.5h;球磨后加入异相包裹材料,在转速为2200rpm的条件下继续球磨3h,最后在温度为180℃的条件下烘干8h,再在进风温度为220℃、出风温度为110℃的条件下喷雾干燥,制得紫色陶瓷色料粉粒。
实施例
实施例1
一种紫色氧化锆陶瓷,包括占紫色氧化锆陶瓷总质量80%的氧化锆粉体和占紫色氧化锆陶瓷总质量20%的紫色陶瓷色料粉粒,所述紫色陶瓷色料粉粒为制备例1制得的紫色陶瓷色料粉粒;所述氧化锆粉体为含有1mol%Al2O3、15mol%Y2O3的钇稳定氧化锆粉体VK-R30Y3。
所述紫色氧化锆陶瓷的制备包括如下步骤:
步骤(1)、球磨及干燥:将氧化锆粉体和制备例1制得的紫色陶瓷色料粉粒混合,得到混合陶瓷料,并加入至球磨设备的料筒中,然后按照混合陶瓷料与水的重量比为1:1.0加入纯水,并加入占混合陶瓷料重量0.1%的聚丙烯酸铵分散剂5027,再加入直径的锆球,球磨锆球添加体积占研磨料筒的研磨腔体积的40%,再将料筒置于砂磨机中,在转速为 900rpm的条件下球磨8h,得到浆料状态的球磨料;最后将球磨料进行喷雾干燥处理,控制喷雾干燥的进风温度为180℃,出风温度为100℃,得到干粒状态的干燥陶瓷粒;
步骤(2)、混炼熔化及密炼:将占干燥陶瓷粒总质量的2%的环氧树脂、占干燥陶瓷粒总质量的7%的邻苯二甲酸二丁酯、占干燥陶瓷粒总质量的0.5%的油酸和占干燥陶瓷粒总质量的 1%的高密度聚乙烯添加至油浴恒温设备中混炼熔化,控制混炼熔化的加热温度为50℃,时间为8h;然后分批加入步骤(1)得到的干燥陶瓷粒,混合均匀后加入至密炼设备中充分剪切、挤压,密炼1h,出料,制得颗粒状的注塑喂料;
步骤(3-1)、注塑成型:将步骤(2)制得的颗粒状注塑喂料加入至注塑机中,当注塑喂料受热熔融呈胶状浆料后进行注塑,通过模具成型生坯,控制溶胶温度为50℃,射胶时间为 15s,模具温度为50℃,注塑速度为20cm3/s,注塑压力为20T,最后冷却、脱模,冷却时间为1s,制得陶瓷生坯;
步骤(3-2)、脱脂、排胶及烧结:将步骤(3-1)制得的陶瓷生坯在温度为300℃的条件下脱脂24h,然后再在温度为400℃的条件下排胶12h,最后在温度为1350℃的条件下保温6h进行烧结处理,制得紫色氧化锆陶瓷;
步骤(4)、CNC及抛光:利用CNC对成型产品进行披锋,去除产品外形余量,然后利用滚抛的方式对产品的内外表面抛光4h,制得紫色氧化锆陶瓷成品。
实施例2-5
实施例2-5与上述实施例1的区别在于紫色陶瓷色料粉粒的来源以及制备陶瓷产品的工艺条件差异,具体参见下表3;
表3实施例1-5的物料种类、物料用量及工艺条件
对比例
对比例1
本对比例与上述实施例3的区别在于:所述紫色陶瓷色料粉粒采用制备对比例6制得的紫色陶瓷色料粉粒。
对比例2
本对比例与上述实施例3的区别在于:所述紫色陶瓷色料粉粒采用制备对比例7制得的紫色陶瓷色料粉粒。
对比例3
本对比例与上述实施例3的区别在于:所述紫色陶瓷色料粉粒采用制备对比例8制得的紫色陶瓷色料粉粒。
对比例4
本对比例与上述实施例3的区别在于:所述紫色陶瓷色料粉粒采用制备对比例9制得的紫色陶瓷色料粉粒。
性能检测试验
(一)物理性能
将上述实施例1-5与对比例1-4制得的紫色氧化锆陶瓷产品抗弯强度、硬度、韧性和密度等性能测试,测试结果参见下表4;所述抗弯强度按照标准《GB/T 4741-1999陶瓷材料抗弯强度试验方法》进行测定,所述硬度按照标准《GB/T 16534-2009精细陶瓷室温硬度试验方法》进行测定;所述韧性按照《GB/T 14389-1993工程陶瓷冲击韧性试验方法》进行测定;所述密度按照《GB/T 2413-1980压电陶瓷材料体积密度测量方法》进行测定。
表4实施例1-5与对比例1-4制得的紫色氧化锆陶瓷性能数据
结合实施例1-5及表4可以看出,本申请的紫色氧化锆陶瓷具有优良的抗弯强度、硬度、韧性和密度等性能,综合性能稳定。
而对比例1采用制备对比例6的紫色陶瓷色料粉粒来制备紫色氧化锆陶瓷产品,与对比例1相比,对比例1制得的产品抗弯强度显著下降,原因可能是色料中没有添加尖晶石材料,使得陶瓷产品的强度和硬度下降,可见尖晶石材料的多面体结晶型体对陶瓷产品的强度、硬度有提高作用,且尖晶石材料占色料组分的50-80%,占比较大,将含有大量尖晶石材料的陶瓷色料用于制备陶瓷产品时,对陶瓷产品的强度、硬度等性能均有提升作用。
而对比例3采用制备对比例8的紫色陶瓷色料粉粒来制备紫色氧化锆陶瓷产品,与实施例3相比,对比例3制得的产品抗弯强度下降,原因可能是陶瓷色料没有进行异相包裹处理,表面没有异相包覆层,降低了显色芯粒与氧化锆粉体的结合性,进而降低了显色芯粒中尖晶石材料对陶瓷产品的强度促进作用。
而对比例4采用制备对比例9的紫色陶瓷色料粉粒来制备紫色氧化锆陶瓷产品,与实施例3相比,对比例4制得的产品抗弯强度、硬度明显下降,原因可能是陶瓷色料制备过程中,显色芯粒与异相包裹材料共混后没有进行第二次煅烧,而是采用喷雾干燥的制得色料粉粒,可能使得显色芯粒的表面没有形成稳定的异相包覆层,进而影响含有尖晶石材料的显色芯粒与氧化锆粉体的结合性,导致了强度的下降。
(二)色差测试
对上述实施例1-5与对比例1-4中的陶瓷材料,按照《GB/T 4739-2015日用陶瓷颜料色度测测定方法》测定其烧结前的RGB值,以及烧结处理后的RGB值,测试结果参见下表5。
表5实施例1-5与对比例1-4的陶瓷材料烧结前后的RGB值
结合实施例1-5及表5可以看出,本申请的紫色氧化锆陶瓷在烧结前后,陶瓷的RGB颜色变化不明显,色差小。
而对比例2采用制备对比例7的紫色陶瓷色料粉粒来制备紫色氧化锆陶瓷产品,与实施例3相比,对比例2的陶瓷在烧结前后的RGB值变化明显,存在色差,且烧结前的颜色呈现紫红色,原因可能是色料中没有添加氧化物引起的,使得烧结前的颜色亦不对应所需颜色,烧结后亦存在一定的色差。
综合实施例3、对比例1、对比例2的性能数据,可知将尖晶石材料与氧化物复配使用,可得到RGB(204,0,204)的紫色效果,且烧结后的色差小,产品强度亦较佳,兼备较优异的物理性能和颜色稳定性。而对比例1仅采用氧化物制备显色芯粒,虽然在异相包覆层的包覆保护作用下使得着色成分附着稳定,不易产生色差,但紫色陶瓷产品的强度性能明显下降;而对比例2仅采用尖晶石材料制备显色芯粒,虽然紫色陶瓷产品的强度性能较为稳定,但是烧结前的产品颜色已与所需产品颜色有出入。而实施例3采用尖晶石材料及氧化物复合作为显色芯粒,制得的陶瓷产品既获得预设的颜色,且着色稳定,又提高了陶瓷产品的强度性能。
而对比例3采用制备对比例8的紫色陶瓷色料粉粒来制备紫色氧化锆陶瓷产品,与实施例3相比,对比例3的陶瓷在烧结前后的RGB值变化显著,色差明显,且紫色加深,原因可能是陶瓷色料并不含有异相包覆层,没有采用异相包裹材料进行包裹处理,使得着色成分未能与陶瓷材料结合稳定,导致在烧结后出现明显色差。
而对比例4采用制备对比例9的紫色陶瓷色料粉粒来制备紫色氧化锆陶瓷产品,与实施例3相比,对比例4的陶瓷在烧结前后的RGB值变化显著,色差明显,且紫色加深,原因可能是陶瓷色料制备过程中,显色芯粒与异相包裹材料共混后没有进行第二次煅烧,而是采用喷雾干燥的方式制得陶瓷色料粉粒,可能使得异相包裹材料未能与显色芯粒的表面在高温煅烧下形成稳定晶格状态的色料粉粒,没有形成稳定的异相包覆层,进而影响着色成分与陶瓷材料的结合稳定性,导致烧结前后出现明显色差。
本具体实施例仅仅是对本申请的解释,其并不是对本申请的限制,本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改,但只要在本申请的权利要求范围内都受到专利法的保护。
Claims (9)
1.一种紫色陶瓷色料粉粒,其特征在于:包括显色芯粒和包覆于所述显色芯粒外壁的异相包覆层,所述异相包覆层的含量占紫色陶瓷色料粉粒总质量的0.5-5wt%;所述显色芯粒包括尖晶石材料和氧化物,尖晶石材料的含量占紫色陶瓷色料粉粒总质量的55-91wt%,氧化物的含量占紫色陶瓷色料粉粒总质量的8-40wt%;
所述异相包覆层为SiO2、ZrO2、ZrSiO4、Al2O3中的一种或者多种的组合;
所述氧化物为氧化硒、氧化铬、氧化铜、氧化镧、氧化铁中的一种或者多种的组合;
该紫色陶瓷色料粉粒的制备包括如下步骤:
A、球磨及干燥:按照重量百分比,将尖晶石材料、氧化物混合,得到混合粉体,并加入至研磨设备中,然后按照混合粉体与水的重量比为1:1.0-1.5加入纯水,再加入占混合粉体重量的0.1-1.0%的聚丙烯酸铵类分散剂,进行球磨,再烘干处理,得到球磨料;
B、第一次煅烧、粉碎和过筛:将步骤A的球磨料进行第一次煅烧,再将煅烧后的粉体粉碎,过筛后得到显色芯粒;
C、异相包裹和第二次煅烧:按照显色芯粒与水的重量比为1:1-3先将纯水加入至研磨设备中,然后加入占显色芯粒重量的0.1-1.5%的双性表面活性剂,搅拌溶解,再加入显色芯粒,球磨1-2h;最后加入异相包裹材料,继续球磨1-5h后烘干、第二次煅烧,过筛后制得紫色陶瓷色料粉粒。
2.根据权利要求1所述的一种紫色陶瓷色料粉粒,其特征在于:所述尖晶石材料为钇铝尖晶石、镱铝尖晶石、钐铝尖晶石、镧锆尖晶石、钴铝尖晶石的一种或者多种的组合。
3.根据权利要求1所述的一种紫色陶瓷色料粉粒,其特征在于:所述步骤A中,加入聚丙烯酸铵类分散剂后球磨的转速为900-3600rpm,球磨时间为1-6h;球磨后烘干的温度为100-250℃,烘干时间为5-15h。
4.根据权利要求1所述的一种紫色陶瓷色料粉粒,其特征在于:所述步骤B中,第一次煅烧的温度为1000-1400℃,保温时间为1-8h;粉碎至显色芯粒至少可过400目筛。
5.根据权利要求1所述的一种紫色陶瓷色料粉粒,其特征在于:所述步骤C中,所述双性表面活性剂为卵磷脂;异相包裹材料为硝化物、氯化物和有机硅中的一种或者多种的组合,所述硝化物为Zr(NO3)4,所述氯化物为AlCl3,所述有机硅为氨基硅烷。
6.根据权利要求1所述的一种紫色陶瓷色料粉粒,其特征在于:所述步骤C中,加入纯水、双性表面活性剂和显色芯粒后的球磨转速为600-1500rpm;加入异相包裹材料后的球磨转速为900-3600rpm;球磨后的烘干温度为100-250℃,烘干时间为4-12h;第二次煅烧的温度为500-800℃,第二次煅烧的时间为1-3h;第二次煅烧后的过筛目数为紫色陶瓷色料粉粒至少可过400目筛。
7.一种紫色氧化锆陶瓷,其特征在于:由包括氧化锆粉体和紫色陶瓷色料粉粒烧结而成,所述氧化锆粉体占紫色氧化锆陶瓷质量的80-95%,紫色陶瓷色料粉粒占紫色氧化锆陶瓷质量的5-20%;所述紫色陶瓷色料粉粒为权利要求1-6任一项所述的紫色陶瓷色料粉粒,所述氧化锆粉体为含有0-20mol% Al2O3、1-15mol% Y2O3的钇稳定氧化锆粉体。
8.一种权利要求7所述的紫色氧化锆陶瓷的制备方法,其特征在于:包括如下步骤:
步骤(1):将氧化锆粉体和紫色陶瓷色料粉粒混合,得到混合陶瓷料,然后将混合陶瓷料与水按照重量比为1:1.0-1.7混合,并加入占混合陶瓷料重量的0.1-1.0%的聚丙烯酸铵类分散剂,在转速为900-3600rpm的条件下球磨1-8h,然后进行喷雾干燥处理,得到干燥陶瓷粒;
步骤(2):往步骤(1)得到的干燥陶瓷粒添加助剂,然后混炼熔化、密炼,制得密炼料;
步骤(3):将步骤(2)制得的密炼料依次进行注塑、脱脂、排胶、烧结,除去聚丙烯酸铵类分散剂及助剂成分,制得紫色氧化锆陶瓷。
9.根据权利要求8所述的一种紫色氧化锆陶瓷的制备方法,其特征在于:所述步骤(1)中,喷雾干燥的进风温度为180-260℃,出风温度为100-130℃;
所述步骤(2)中,混炼熔化过程中添加的助剂包括粘接剂、增塑剂、润滑剂和骨架剂,混炼熔化的温度为50-150℃,混炼熔化的时间为0.5-8h,密炼的时间为1-8h;
所述步骤(3)中,注塑过程为当密炼料受热熔融呈胶状浆料后进行注塑,溶胶温度为50-200℃,射胶时间为1-15s,模具温度为50-250℃,注塑速度为3-20cm3/s,注塑压力为20-200T,冷却时间为1-12s;
所述步骤(3)中,脱脂的温度为300-450℃,脱脂时间为12-24h;排胶的温度为400-600℃,排胶时间为4-12h;烧结处理是在温度为1350-1550℃的条件下保温2-6h。
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