CN108910856B - 一种含磷酸钛钙及钛氢磷酸盐双晶相的多孔材料的制备方法及所得产品 - Google Patents
一种含磷酸钛钙及钛氢磷酸盐双晶相的多孔材料的制备方法及所得产品 Download PDFInfo
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- 239000011148 porous material Substances 0.000 title claims abstract description 43
- 239000013078 crystal Substances 0.000 title claims abstract description 26
- PSKMQMATIKSZEV-UHFFFAOYSA-H calcium titanium(4+) diphosphate Chemical compound [Ca+2].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O PSKMQMATIKSZEV-UHFFFAOYSA-H 0.000 title claims abstract description 20
- JWFYORYPRRVBPH-UHFFFAOYSA-J hydrogen phosphate;titanium(4+) Chemical compound [Ti+4].OP([O-])([O-])=O.OP([O-])([O-])=O JWFYORYPRRVBPH-UHFFFAOYSA-J 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000010791 quenching Methods 0.000 claims abstract description 11
- 230000000171 quenching effect Effects 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000005260 corrosion Methods 0.000 claims description 10
- 230000007797 corrosion Effects 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 229910009973 Ti2O3 Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 17
- 238000001179 sorption measurement Methods 0.000 abstract description 11
- 238000005342 ion exchange Methods 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 3
- 238000005530 etching Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000000975 bioactive effect Effects 0.000 abstract 1
- -1 heat treating Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- 239000001506 calcium phosphate Substances 0.000 description 4
- 229910000389 calcium phosphate Inorganic materials 0.000 description 4
- 235000011010 calcium phosphates Nutrition 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 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 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AQVJBQZLOYEZEP-UHFFFAOYSA-H P(=O)([O-])([O-])[O-].[Ti+4].[Cu+2].P(=O)([O-])([O-])[O-] Chemical compound P(=O)([O-])([O-])[O-].[Ti+4].[Cu+2].P(=O)([O-])([O-])[O-] AQVJBQZLOYEZEP-UHFFFAOYSA-H 0.000 description 1
- 229910010254 TiO2—P2O5 Inorganic materials 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003462 bioceramic Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HJGOHDIBOLULKU-UHFFFAOYSA-K calcium copper phosphate Chemical compound P(=O)([O-])([O-])[O-].[Ca+2].[Cu+2] HJGOHDIBOLULKU-UHFFFAOYSA-K 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- C01B25/26—Phosphates
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Abstract
本发明公开了一种含磷酸钛钙及钛氢磷酸盐双晶相的多孔材料的制备方法及所得产品,该多孔材料由15‑30mol%CaO,25‑40mol%CuO,15mol%TiO2和30mol%P2O5制成,制备时,先将各原料熔融,然后经急冷成型或水淬、热处理、酸蚀等步骤得到。该方法生产周期短,适合工业化应用推广和大规模生产。所得多孔材料同时含有磷酸钛钙及钛氢磷酸盐晶相,有望用做具有吸附和离子交换功能的生物活性材料。
Description
技术领域
本发明涉及一种含磷酸钛钙及钛氢磷酸盐双晶相的多孔材料的制备方法及所得产品,属于多孔材料技术领域。
背景技术
磷酸钙及钛基材料是生物领域最用的生物材料,它们的生物毒性低,可用作植入体和载体材料。磷酸钙可用于修饰钛基材料,以提高后者的生物活性。将磷酸钙做成多孔材料有助于与生物体的嵌合,加强传质过程。但同时含有磷酸钙及钛元素的材料报道不多,主要有CeO2促进结晶(F. Soleimani, M. Rezvani, Materials Research Bulletin, 2012,47 : 1362-1367)和CaO-Al2O3-TiO2-P2O5系统中 (S. Banijamali等, Journal of Non-crystalline Solids, 2012,358:303-309)制得的磷酸钙钛[CaTi4 (PO4)6]微晶玻璃以及溶胶-凝胶法合成的CaTi4 (PO4)6(M. Dressler等,Journal of Sol-Gel Science andTechnology, 2012, 62:273–280)等,而低钙的Ca0.5(Ti2P3O12)更是鲜见合成报道(Structure Types. Part 8: Space Groups (156)P3m1 – (148)R-3 ·Ca0.5(Ti2P3O12))。提高磷酸钙钛材料的活性也是材料学者关注的方向。如赵中伟等报道了磷酸钙钛生物陶瓷膜(材料导报,2008,22:125-128)经碱处理后,有助于诱导羟基磷灰石的沉积,达到了提高生物活性的目的。如能在此类材料中引入离子交换功能(如引入具有优异离子交换功能的钛氢磷酸盐相),将有助于进一步提高材料的生物活性,有望主动诱导羟基磷灰石在材料孔隙中生成,为生物材料的性能调控提供新的途径。
发明内容
本发明旨在提供了一种含磷酸钛钙及钛氢磷酸盐双晶相的多孔材料的制备方法及所得产品,该方法基于多相固体经选择性酸腐蚀合并原位重组原理,制得了含磷酸钛钙及钛氢磷酸盐双晶相的多孔材料,该方法操作简单易控,便于规模化生产,所得材料具有较高的比表面积大,具有吸附和离子交换功能,有利于生物应用。
本发明具体技术方案如下:
一种含磷酸钛钙及钛氢磷酸盐双晶相的多孔材料的制备方法,该方法包括以下步骤:
(1)按照CaO 15~30mol%、CuO 25~40mol%、TiO2 15mol%、P2O530mol%的组分含量称取各原料;
(2)将各原料混合均匀,得混合料,将混合料升温至熔融,所得熔融液在模具上急冷成型或水淬;
(3)将急冷成型的样品冷却,或将水淬的样品干燥,备用;
(4)将步骤(3)的样品先在530-550℃下保温,再在680-715℃下保温;
(5)将步骤(4)的样品浸在盐酸中进行腐蚀,得到含锐钛型TiO2相的多孔材料。
进一步的,步骤(1)中,提供CaO、CuO、TiO2 组分的原料为各氧化物,即氧化钙、氧化铜、二氧化钛,提供P2O5组分的原料可以直接是氧化物P2O5,也可以是磷酸溶液。配方中,各组分的总摩尔量为100%。
进一步的,步骤(2)中,当采用磷酸溶液引入P2O5时,先将其他固体粉状原料混合均匀,再加入磷酸溶液和水混合均匀,混合均匀后加热处理,然后粉碎,得混合料;当采用P2O5粉料引入P2O5时,直接将各原料混合均匀即可得混合料。其中,加热处理时,在200℃处理24小时。
进一步的,步骤(2)中,混合料按照一定的升温程序进行升温熔融,升温程序为:先以5-10℃/min的升温速率从室温升到700℃,然后以3-5℃/min的升温速率从700℃升到1250℃,并在1250℃保温使混合料完全熔融。
进一步的,步骤(3)中,将急冷成型的样品冷却至530-550℃,直接在此温度下进行第一段保温处理,或者将急冷成型的样品直接冷却至室温,然后再升至530-550℃进行第一段保温处理。
进一步的,步骤(4)中,样品在530-550℃下保温1小时,再在680-715℃下保温2小时。
进一步的,步骤(5)中,盐酸的浓度为0.5-1.5mol/L;盐酸腐蚀时优选在高温下进行,腐蚀温度为70-90℃,一般腐蚀时间为24小时。
本发明含磷酸钛钙及钛氢磷酸盐双晶相的多孔材料形成机理为:首先,各原料组分在高温熔融状态下充分反应,经急冷成型或水淬固化无定型态的不透明黑色块体或颗粒。块体或颗粒进行两段式保温热处理,以促进成核和晶体生长,从而再结晶析出磷酸钛铜、焦磷酸铜、磷酸铜、磷酸铜钙等晶相,含这些晶相的多相块体或颗粒在热盐酸溶液中处理,晶相受腐蚀速度和受腐蚀程度不同,在腐蚀的同时还发生有复杂的原位化学反应,最终形成含有磷酸钛钙及钛氢磷酸盐双晶相的多孔材料。
进一步的,本发明所得多孔材料为块状或颗粒状,其中采用急冷成型的产品形貌为块状,水淬产品的形貌为颗粒状。结合XRD、EDS、NMR结果分析可知,该多孔材料含磷酸钛钙[Ca0.5(Ti2P3O12)]及钛氢磷酸盐[Ti2O3(H2PO4)2·2H2O]双晶相,根据各晶相衍射峰的数量和相对强弱判断,前者是主晶相,具有生物活性;后者为次晶相,因含氢离子而具有离子交换功能。
进一步的,本发明多孔材料的多孔来源于晶相颗粒之间的空隙。孔径分布较宽,在介孔到大孔范围内分布。这些孔是在两段式热处理形成的晶相酸蚀时发生选择性溶出、并重新生成新物相的同时产生的。孔的存在有利于材料吸附其它物质。
本发明多孔材料制备过程易产业化,所得材料具有较高的比表面积,孔径在介孔至大孔范围分布,具有吸附、离子交换功能。因此,上述方法制得的含磷酸钛钙及钛氢磷酸盐双晶相的多孔材料也在本发明保护范围之内。
本发明先通过熔融、热处理、酸蚀等步骤制得含磷酸钛钙及钛氢磷酸盐双晶相的多孔材料,该方法步骤紧凑,适合工业化应用推广和大规模生产,为多孔磷酸钛钙材料制备技术提供了全新的思路。所得多孔材料具有生物活性,同时具有吸附、离子交换功能,可望用做药物载体或生物填充材料。
附图说明
图1为实施例1-4所得样品的XRD衍射图谱。
图2 为实施例1所得样品的N2吸附等温曲线。
图3为实施例1所得样品的BJH孔径分布曲线。
具体实施方式
下面结合附图和具体实施例对本发明做进一步说明,下述说明仅是示例性的,并不对其内容进行限制。
采用氮气等温吸附仪 (Autosorb iQ-C) 测定样品N2等温吸附曲线,根据BET模型计算比表面积,根据BJH模型得孔径分布曲线,并由曲线峰值点数据确定主孔径,孔容由N2吸附曲线相对压力最大处的吸附量确定。
实施例1
1、按照CaO15%、CuO40%、TiO215%、P2O530%的摩尔组成选择原料,CaO、CuO、TiO2的原料为氧化物本身,P2O5的原料为磷酸溶液(85wt%)。
2、将氧化钙、氧化铜和氧化钛粉状原料混合均匀,再加入磷酸溶液和适量水,混合均匀,在200℃下加热24小时,粉碎备用,得混合料。
3、将步骤2的混合料放入坩埚中,以10℃/min的升温速率从室温升到700℃,然后以5℃/min的升温速率从700℃升到1250℃,并在1250℃保温1h,使混合料完全熔融,将熔融态的样品倒出到模具上急冷成型得块状样品,块状样品冷却至室温备用。
4、将样品以5℃/min的升温速率升至530℃,并保温1h,然后以5℃/min的升温速率由530℃升至680℃,保温2h。保温结束后样品随炉冷却至室温。
5、将步骤4得到的样品在80℃的1mol/L的盐酸中浸泡24h,取出,得到含Ca0.5(Ti2P3O12)及Ti2O3(H2PO4)2·2H2O双晶相(见图1)多孔材料。
经N2等温吸附分析,产品的BET表面积为36m2/g,孔容为0.18cm3/g;如图3所示,材料中孔径分布较宽,在介孔到大孔范围内分布;N2吸附测得的主孔径为17.4nm,还有部分孔集中在2-5nm。
实施例2-4
实施例2-4的组成、两段式热处理温度及所得材料的表面积、孔容、主孔径如表1所示。其余步骤及特征与实施例1相同。
实施例2 | 实施例3 | 实施例4 | |
CaO | 20 | 25 | 30 |
CuO | 35 | 30 | 25 |
TiO<sub>2</sub> | 15 | 15 | 15 |
P<sub>2</sub>O<sub>5</sub> | 30 | 30 | 30 |
第一段热处理温度 (<sup>o</sup>C) | 540 | 545 | 550 |
第二段热处理温度 (<sup>o</sup>C) | 682 | 695 | 715 |
表面积(m<sup>2</sup>·g<sup>-1</sup>) | 60 | 57 | 44 |
孔容(cm<sup>3</sup>·g<sup>-1</sup>) | 0.31 | 0.37 | 0.29 |
主孔径(nm) | 30.3 | 30.3 | 30.1 |
Claims (10)
1.一种含磷酸钛钙及钛氢磷酸盐双晶相的多孔材料的制备方法,其特征是包括以下步骤:
(1)按照CaO 15~30mol%、CuO 25~40mol%、TiO2 15mol%、P2O5 30mol%的组分含量称取各原料;
(2)将各原料混合均匀,得混合料,将混合料升温至熔融,所得熔融液在模具上急冷成型或水淬;
(3)将急冷成型的样品冷却,或将水淬的样品干燥,备用;
(4)将步骤(3)的样品先在530-550℃下进行第一段保温,再在680-715℃下进行第二段保温;
(5)将步骤(4)的样品浸在盐酸中进行腐蚀,得到含磷酸钛钙及钛氢磷酸盐双晶相的多孔材料。
2.根据权利要求1所述的制备方法,其特征是:CaO、CuO、TiO2组分由各自的氧化物引入,P2O5组分由其氧化物P2O5 或磷酸溶液引入。
3.根据权利要求1所述的制备方法,其特征是:步骤(2)中,当采用磷酸溶液引入P2O5时,先将其他固体粉状原料混合均匀,再加入磷酸溶液和水混合均匀,混合均匀后在200℃加热处理24小时,然后粉碎,得混合料。
4.根据权利要求1所述的制备方法,其特征是:步骤(2)中,当采用P2O5粉料引入P2O5时,直接将各原料混合均匀即可得混合料。
5.根据权利要求1所述的制备方法,其特征是:步骤(2)中,熔融时,先以5-10℃/min的升温速率从室温升到700℃,然后以3-5℃/min的升温速率从700℃升到1250℃,并在1250℃保温1小时使混合料完全熔融。
6.根据权利要求1所述的制备方法,其特征是:步骤(3)中,将急冷成型的样品冷却至530-550℃,直接在此温度下进行第一段保温处理,或者将急冷成型的样品直接冷却至室温,然后再升至530-550℃进行第一段保温处理。
7.根据权利要求1所述的制备方法,其特征是:步骤(4)中,样品在530-550℃下保温1小时,在680-715℃下保温2小时。
8.根据权利要求1所述的制备方法,其特征是:步骤(5)中,盐酸的浓度为0 .5-1.5mol/L,腐蚀时的温度为70-90℃,腐蚀时间为24小时。
9.根据权利要求1-8中任一项所述的制备方法制得的含磷酸钛钙及钛氢磷酸盐双晶相的多孔材料,其特征是:所述含磷酸钛钙及钛氢磷酸盐双晶相的多孔材料为块状或颗粒状,具有介孔和大孔。
10.根据权利要求1-8中任一项所述的制备方法制得的含磷酸钛钙及钛氢磷酸盐双晶相的多孔材料,其特征是:主晶相为Ca0 .5(Ti2P3O12),次晶相为Ti2O3(H2PO4)2·2H2O。
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