CN101891455B - 一种中低温烧结精骨瓷及其生产方法 - Google Patents
一种中低温烧结精骨瓷及其生产方法 Download PDFInfo
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- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 238000010304 firing Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 16
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 13
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 9
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010433 feldspar Substances 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 238000009766 low-temperature sintering Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 7
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 7
- 239000004571 lime Substances 0.000 claims description 7
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052863 mullite Inorganic materials 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 235000015895 biscuits Nutrition 0.000 abstract 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- 239000003245 coal Substances 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
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- 230000004927 fusion Effects 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
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- 229910052573 porcelain Inorganic materials 0.000 description 63
- 108010048734 sclerotin Proteins 0.000 description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- 229910052799 carbon Inorganic materials 0.000 description 20
- 239000000843 powder Substances 0.000 description 12
- 239000012071 phase Substances 0.000 description 11
- 239000010453 quartz Substances 0.000 description 7
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- 238000002834 transmittance Methods 0.000 description 5
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
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- 239000010456 wollastonite Substances 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910001038 basic metal oxide Inorganic materials 0.000 description 1
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- 229940036811 bone meal Drugs 0.000 description 1
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- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
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Abstract
本发明涉及一种中低温烧结精骨瓷及其生产方法，该瓷的化学组成为：SiO252～60％，Al2O328～37％，K2O 1～4％，Na2O 1～2％，CaO 3～8％，MgO 1～3％，P2O51～3％，所用的原料配方为：骨灰3～8％、高岭土32～45％、氧化铝10～20％、熔块35～50％，烧结温度为1170℃～1250℃，既可以采用“高温素烧、低温釉烧”或“低温素烧、高温釉烧”的二次烧成工艺，也可以应用高温一次烧成工艺。本发明的精骨瓷具有传统骨质瓷的外观效果，而理化性能优于骨质瓷，具有骨碳用量少、烧结温度低的突出优点，有利于降低生产成本和能源消耗。
Description
技术领域
本发明属于日用陶瓷制造技术领域，具体涉及一种中低温烧结精骨瓷及其生产方法。
背景技术
骨质瓷是18世纪英国人发明的一种软质瓷，它以骨碳为主，加入部分粘土、长石、石英等矿物原料，采用高温素烧(1250℃～1280℃)、低温釉烧(1100℃～1150℃)的二次烧成工艺烧制而成。骨质瓷具有白度高、透光度好、瓷质细腻等突出优点，是举世公认的高档日用细瓷。我国20世纪70年代研究和开发了部分骨质瓷产品，到20世纪80年代以后，我国的唐山、淄博、景德镇和潮州等地区先后进行了批量生产。
然而，骨质瓷也存在以下一些固有的缺点：1)热稳定性差，骨质瓷热稳定性的国家标准是140℃～20℃热交换一次不裂，远低于日用细瓷180℃～20℃热交换一次不裂的标准，这是由于骨质瓷的主晶相磷酸钙和钙长石的热膨胀系数较高造成的；2)烧成范围窄，其原因是骨质瓷的组成位于磷酸三钙、钙长石和石英的三元最低共熔点(1290℃)附近，当温度低于最低共熔点时，瓷坯中液量很少，制品无法烧结，而温度达到或高于最低共熔点时，大量液相同时产生，导致产品极易软化变形，因此，烧成难以控制，这也是骨质瓷通常必须采用二次烧成工艺(通过仿型匣钵进行高温素烧和低温釉烧)的原因；3)釉面硬度低，其根源是采用了适合于低温釉烧的熔块釉；4)坯料成本高，传统骨质瓷坯料中骨碳的用量一般为40～60％，由于使用骨碳的价格高，导致骨质瓷坯料成本居高不下。随着我国骨质瓷生产规模的扩大，骨碳的需求量不断攀升，导致骨碳供应紧张，价格上涨，这直接影响到骨质瓷的进一步发展。
因此，降低骨质瓷坯料的骨碳用量，开发具有骨质瓷外观效果的新瓷种，这是骨质瓷发展的一种战略选择。20世纪80年代，日本陶瓷工作者部分使用，甚至不使用骨碳，研发了外观质量接近骨质瓷的陶瓷产品，这类产品透光度好、色调柔和，称为“新骨瓷”。20世纪90年代以来，我国也逐步开展了这类产品的研发。减少骨碳用量通常采用的技术路线有两种，其一是用天然磷灰石作原料代替骨碳。CN1072916A公开了一种利用磷灰石生产骨灰瓷的工艺方法，以磷灰石全部代替骨碳，采用传统高温素烧(1240℃～1260℃)、低温釉烧两次烧成工艺，其配方组成为：磷灰石35～60％、滑石2～5％、石英10～15％、长石8～13％。减少骨碳用量的另一种技术路线就是增加石英、瓷石以及氧化铝来减少骨碳用量。ZL95112612.1公开了一种“强化骨灰瓷”的生产工艺，它通过大幅提高石英和石英玻璃的用量来实现降低骨碳用量，其配方组成为：骨灰或磷灰石用量5～15％、硅灰石5～15％、石英30～40％、石英玻璃10～20％、粘土20～25％、增塑剂1～5％、滑石1～4％，其主要晶相为α-方石英，次晶相为β-Ca3(PO4)2、钙长石和硅灰石，烧成温度为1220℃～1300℃。ZL200610031882.3公开的一种“新型骨灰瓷及其生产方法”则是采用大量的瓷石和少量氧化铝粉，其配方组成为：骨灰5～10％、高岭25～35％、瓷石45～60％、铝粉5～10％，其主晶相为莫来石，次晶相为β-Ca3(PO4)2和钙长石，烧成温度为1230℃～1300℃，氧化焰中烧成。大量应用氧化铝粉降低骨碳用量的是ZL200610034842.4公开的一种骨质强化瓷及其生产工艺，其配方组成为：合成骨粉8～12％、α-氧化铝粉20～25％、龙岩洗泥45～50％、湖南长石13～15％，贵州粘土5～8％，烧成温度为1260℃～1280℃。CN1210833A公开了一种新骨质瓷及其生产方法：在长石质瓷配方基础上加入2～10％的骨灰，烧成温度为1325℃～1340℃。本发明通过配方设计和工艺优化，进一步减少了骨碳用量，骨碳含量仅为3～8％，烧成温度降至1170℃～1250℃，克服了传统骨质瓷烧成温度范围窄、容易变形等缺点，瓷质达到了骨质瓷的外观效果，而且理化性能优于骨质瓷。正是由于本发明的骨质瓷所用骨碳量少而性能好，达到了“少而精”的目标，因此本发明的骨质瓷又称为“精骨瓷”。
发明内容
本发明的目的在于克服现有骨质瓷存在的固有缺点，提供一种中低温烧结精骨瓷及其生产方法。
本发明提供的一种中低温烧结精骨瓷，其特征在于其化学组成按重量比为：SiO252～60％，Al2O328～37％，K2O1～4％，Na2O1～2％，CaO 3～8％，MgO1～3％，P2O51～3％，根据瓷坯的化学组成得出的坯式如下：
精骨瓷的主晶相为莫来石，次晶相为钙长石，它不但保持了传统骨质瓷透光度好、瓷质细腻、高雅洁白等特点，而且理化性能如热稳定性、釉面硬度以及热膨胀系数优于骨质瓷。
本发明提供的中低温烧结精骨瓷既可以采用传统骨质瓷“高温素烧、低温釉烧”或“低温素烧、高温釉烧”的二次烧成工艺，也可以像普通日用细瓷那样应用高温一次烧成工艺，其特征在于所用的原料配方按重量比为：骨灰3～8％、高岭土32～45％、氧化铝10～20％、熔块35～50％，所用的熔块的化学组成为：SiO275～85％，Al2O35～9％，CaO3～7％，MgO2～6％，K2O2～4％，Na2O1～3％；烧结温度范围为1170℃～1250℃。
李家驹主编的《陶瓷工艺学》(中国轻工业出版社出版，2001年第1版，P98)给出的骨质瓷坯料配方为：骨灰20～60％、长石8～22％、高岭土25～45％、石英9～20％，与此相比，本发明的精骨瓷坯料配方有三个突出特点：一是骨灰用量少，二是用氧化铝取代石英，三是不用长石而采用熔块作熔剂。
本发明中的氧化铝粉加入量是非常关键的，如果像ZL200610031882.3那样只加入5～10％的氧化铝粉，则其改性效果不佳；反之，如果像ZL200610031882.3那样加入20～25％的氧化铝粉，则不但会明显提高坯体的烧成温度，而且还会显著降低瓷坯的透光性能，结果就根本达不到传统骨质瓷的透光效果。
本发明在坯体配方中引入10～20％氧化铝粉为改性剂，一方面可以提高瓷胎强度、白度和热稳定性，另一方面又可以扩大瓷坯烧结范围和减小坯体高温变形度。Al2O3颗粒本身的强度高，它单独存在时，可以均匀地分布在瓷胎中起到颗粒弥散增强的作用，提高坯体的抗高温变形性能。部分Al2O3颗粒还可以和由高岭土脱水分解后所产生的SiO2反应，结果生成机械强度高、膨胀系数小的莫来石晶体，这对提高瓷胎强度和热稳定性是十分有利的。部分Al2O3颗粒在高温下溶入瓷坯的液相中，可提高液相的高温粘度，有利于扩大坯体的烧成范围。
本发明的一个突出创新之处在于坯料中引入了熔块而不是采用长石作为熔剂。本发明的熔块与长石相比，其化学组成有两个显著特点。第一个特点是熔块的SiO2含量高达75～85％，比长石63～71％的含硅量高得多，这就使得本发明的熔块的高温粘度比长石熔体的粘度高得多，而且随着温度的升高，熔块高温粘度的变化比长石熔体小，因此使用本发明的熔块作熔剂比应用长石更有利于扩大坯体的烧成范围。高SiO2含量的熔块在骨质瓷坯中还发挥着两个重要作用：一是高硅熔块热膨胀系数小，有利于降低骨质瓷的热膨胀系数，提高骨质瓷的热稳定性能；二是高硅熔块具有透明度高和机械强度大的优点，有利于提高骨质瓷的透光度和力学性能。本发明的熔块具有的第二个特点是熔块的化学组成同时含有碱金属和碱土金属氧化物，利用两者的协同助熔作用可使坯体的烧成温度大为降低，而使用长石作为熔剂，由于长石只含有碱金属氧化物，因此其助熔作用就不及本发明的熔块。
本发明的精骨瓷中虽然骨碳含量降至3～8％，但是它仍能保持骨质瓷的透光度好、瓷质细腻、高雅洁白等特点。如果像CN1072916A那样完全不用骨碳，则瓷坯的质感就大打折扣，结果就失去了骨质瓷的外观效果。
传统骨质瓷的主晶相为β-Ca3(PO4)2和钙长石，由于主晶相的膨胀系数较大，因此骨质瓷的膨胀系数高达8.0～8.5×10-6/℃(RT～500℃)，导致骨质瓷的热稳定性较差；本发明的精骨瓷的主晶相为莫来石，次晶相为钙长石，由于莫来石的膨胀系数较小，这就使得精骨瓷的膨胀系数较低，其值为4.5～5.2×10-6/℃(RT～500℃)，因此，精骨瓷具有热稳定性好的优点，精骨瓷经200℃～20℃热交换一次不裂。
本发明的中低温烧结精骨瓷与现有骨质瓷相比有三个明显的优势：一是烧结温度低，烧结温度范围为1170℃～1250℃，而且可以一次高温烧成，与传统骨质瓷的烧结范围1220℃～1280℃和二次烧成工艺相比，显著降低了能耗，同时还有利于提高窑炉的使用寿命；二是骨碳用量少，仅为3～8％，精骨瓷保持了传统骨质瓷透光度好、瓷质细腻、高雅洁白等特点，大大降低了骨质瓷的原料成本，对扩大骨质瓷的生产和应用具有重要意义；三是理化性能好，优化的氧化铝粉用量使精骨瓷不但透光性能好，而且其机械强度和热稳定性均优于骨质瓷。
具体实施方式
实施例1：
按坯料配方称取各种原料：骨灰3％，高岭43％，氧化铝粉17％，熔块37％，坯料的化学组成为：SiO253.69％，Al2O337.07％，Fe2O30.13％，CaO3.29％，MgO 1.12％，K2O 2.40％，Na2O 1.03％，P2O51.27％，熔块的化学组成为：SiO279.41％，Al2O38.10％，CaO 3.87％，MgO 2.64％，K2O 3.33％，Na2O2.57％。将上述原料投入球磨机内，混合球磨至所要求的细度(塑性泥要求细度为＜10μm占75～80％，注浆泥要求细度为＜10μm占75左右)。然后，依次进行过筛、除铁、压滤、练泥、陈腐、成型，然后在1200℃～1250℃素烧，素烧坯体经抛光捡选后施熔块釉，再在1100℃～1130℃釉烧，最后得到精骨瓷。如果是采用一次烧成工艺，那么坯体成型后施生料釉，然后在1200℃～1250℃温度下烧成即可。
实施例2：
按坯料配方称取各种原料：骨灰5％，高岭40％，氧化铝粉13％，熔块42％。坯料的化学组成为：SiO256.48％，Al2O331.06％，Fe2O30.12％，CaO5.44％，MgO 1.93％，K2O 1.96％，Na2O 0.87％，P2O52.13％，熔块的化学组成为：SiO280.65％，Al2O35.29％，CaO 5.69％，MgO 4.27％，K2O 2.10％，Na2O1.92％。烧成温度1190℃～1220℃，其它生产工艺与实施例1相同。
实施例3：
按坯料配方称取各种原料：骨灰7％，高岭35％，氧化铝粉11％，熔块47％。坯料的化学组成为：SiO256.14％，Al2O328.00％，Fe2O30.12％，CaO 7.12％，MgO 2.33％，K2O 2.15％，Na2O 1.14％，P2O52.99％，熔块的化学组成为：SiO277.42％，Al2O36.74％，CaO 6.15％，MgO 4.72％，K2O 2.57％，Na2O 2.31％。烧成温度1170℃～1200℃，其它生产工艺与实施例1相同。
由上述各实施例所制得的精骨瓷性能如下表：
Claims (2)
1.一种中低温烧结精骨瓷，其特征在于其化学组成按重量比为：SiO252～60％，Al2O328～37％，K2O1～4％，Na2O1～2％，CaO3～8％，MgO1～3％，P2O51～3％；其主晶相为莫来石，次晶相为钙长石。
2.一种生产如权利要求1所述中低温烧结精骨瓷的方法，包括采用高温素烧、低温釉烧或低温素烧、高温釉烧的二次烧成工艺，或采用高温一次烧成工艺，其特征在于所用的原料配方按重量比为：骨灰3～8％、高岭土32～45％、氧化铝10～20％、熔块35～50％，其中所述熔块的化学组成为：SiO275～85％，Al2O35～9％，CaO3～7％，MgO2～6％，K2O2～4％，Na2O1～3％；对于采用高温一次烧成工艺，其烧结温度为1170℃～1250℃。
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| CN101891455B (zh) * | 2010-07-08 | 2012-07-18 | 景德镇陶瓷学院 | 一种中低温烧结精骨瓷及其生产方法 |
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| WO2012003792A1 (zh) | 2012-01-12 |
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