Ti radical surface is multilayer exceed fine HA coating compound the preparation that cultivates style

1 material 　 with calcium nitrate [Ca(NO3)2. 4H2O] with phosphoric acid 3 armour fat [(CH3O)3PO] for initiative raw material, prepare 5 identical titanium piece make matrix with root of tooth of a titanium, test job is finished in university of Beijing science and technology. 1.

2 process 　 takes calcium nitrate 11.

8g, phosphoric acid 3 armour fat 4.

2g(quality is than making an appointment with 2.

86 ∶ 1) , value of PH of the preparation in the dissolvent that adds certain amount is 7.

5 sol fluid of the left and right sides, this kind deserves to compare atomic of the Ca that can make sample HA coating pulverous, P rub the than be close to bone most calcic phosphor that Er counts is compared (1.

67 ∶ 1) . this liquid park 65 ℃ fluctuate, after maintaining 30 ～ 60min, get transparent ropy shape rare paste, namely the sol fluid of Ca. Use down to brush a collosol that has matched even ground daub is in fluid to be divided through immersing corrupt metallic titanium piece go up with titanium tooth root, evaporate as solvent, apparently lilquid film forms base material with respect to meeting gelation film of a gel, be worth to maintain PH constant, dry process appropriate controls sol fluid to be finished inside 20min, otherwise gel film has oxidation calcium in agglomeration (CaO) appears. To avoid velar chap, in 70 ～ the condition of 80 ℃ falls after making gel film completely dry, put add Wen Lu, with 15 ℃ / Min speed warms up after 350 ℃ , constant temperature 10min, then with 11 ℃ / the speed of Min warms up 600 ℃ , constant temperature 3 ～ 4h, fall again naturally to room temperature, the feature of T5 of ～ of T1 of sample of the mark after be being taken out, t6 is tooth root, wash T1, T2, T5, T6 with distilled water bubble 40min, t3, T4 not bubble is washed. Repeat afore-mentioned coating agglomeration processes, t4, T5 is done 5 times; T1 is done 10 times; T2, T3, T6 is done 20 times. Reaction equation: 10Ca(NO3) 2. Other of ＋ of Ca10 (PO4) 6 (OH)2 of → of 4H2O ＋ 6(CH3O) 3PO 2 results and the face that discussion 　 uses sample of coating of HA of observation of lens of report of Cantabrigian S250MK3 scanning and lateral form appearance, pat its photograph and XRD a collection of illustrative plates, a collection of illustrative plates is chart of typical crystallization condition HA, the substance appearance composition that it shows sample HA coating basically depends on of raw material deserve to compare, and crystallization is spent and granuality depends on value of sol fluid PH, firing temperature and constant temperature time. T6 of ～ of sample T1 and Japan the parameter of I of sample of company of 3 water chestnut undertakes contrasting, and the diffractive graph of reference standard sample makes trade off study (see a table 1) . The order that arranges sample by purity actor bad is T5, T4, T1, T2 (T6) , T3, among them the purity of T4, T5 and T1 is taller. The XRD diffractive data that expresses coating of 1 sample T1, T2(T6) , T3, T4, T5 and ASTM card data. I/I 0 0 of 　 of I/I 0 D/nm of 　 of I/I 0 D/nm of 　 of I/I 0 D/nm of 　 of I/I 0 D/nm of 　 of I/I 0 D/nm of 　 of T 1 T 2 (T 6) T 3 T 4 T 5 I D/nm I/I 0 D/nm of data of card of Table L XRD Diffraction And ASTM Card Date Of Coat Sample T1, T2 (T6) , T3, T4, T5.

344 　 40 0.

344 　 37 0.

344 　 33 0.

345 　 29 0.

345 　 46 0.

36 0 of 343 　 　 .

33 0 of 343 　 　 .

317 　 11 0.

317 　 11 0.

317 　 10 0.

317 　 12 0.

314 　 20 0.

316 　 15 0.

9 0 of 317 　 　 .

308 　 17 0.

308 　 , 0.

308 　 , 0.

308 　 , 0.

308 　 28 0.

307 　 24 0.

32 0 of 308 　 　 .

281 100 0.

280 100 0.

280 100 0.

281 　 100 0.

281 100 0.

280 　 100 0.

100 0 of 281 　 　 .

278 　 60 0.

278 　 , 0.

278 　 69 0.

278, 0.

278 　 77 0.

277 　 77 0.

58 0 of 278 　 　 .

272 　 60 0.

271 　 62 0.

271 　 60 0.

271 　 67 0.

272 　 61 0.

271 　 70 0.

60 0 of 272 　 　 .

263 　 25 0.

263 　 24 0.

263 　 24 0.

263 　 26 0.

263 　 34 0.

262 　 33 0.

21 0 of 263 　 　 .

253 　 5 0.

252 　 7 0.

7 0 of 252 　 　 .

253 　 , 0.

253 　 , 0.

253 　 , 0.

8 0 of 251 　 　 .

230 　 7 0.

229 　 13 0.

229 　 , 0.

229 　 , 0.

229 　 16 0.

229 　 , 0.

229 　 　 , 0.

226 　 20 0.

225 　 52 0.

225 　 50 0.

226 　 67 0.

226 　 34 0.

225 　 34 0.

24 0 of 226 　 　 .

215 　 9 0.

215 　 8 0.

8 0 of 214 　 　 .

214 　 12 0.

215 　 18 0.

214 　 11 0.

18 0 of 215 　 　 .

207 　 7 0.

206 　 7 0.

8 0 of 206 　 　 .

206 　 12 0.

207 　 16 0.

206 　 14 0.

10 0 of 204 　 　 .

200 　 5 0.

200 　 5 0.

6 0 of 200 　 　 .

200 　 , 0.

200 　 13 0.

200 　 12 0.

9 0 of 200 　 　 .

194 　 30 0.

194 　 34 0.

194 　 28 0.

194 　 48 0.

194 　 37 0.

194 　 38 0.

36 0 of 194 　 　 .

189 　 15 0.

189 　 15 0.

189 　 , 0.

189 　 , 0.

189 　 22 0.

189 　 23 0.

13 0 of 189 　 　 .

187 　 5 0.

187 　 11 0.

187 　 22 0.

187 　 57 0.

187 　 , 0.

187 　 , 0.

187 　 　 , 0.

184 　 40 0.

184 　 29 0.

184 　 31 0.

184 　 48 0.

53 0 of 184 　 　 .

184 　 47 0.

　 of 35 Nextpage of 184 　 　 observes enlarge the 700 times form appearance with powder of coating of the HA in the microstructure photograph of 5000 times, the content of the HA in HA powder is as high as 99.

1 ％ , all matter content under 0.

9 ％ . Coating has bore diameter for 0.

8 ～ 3.

A few stoma of 2 μ M appear, the average porosity of coating sample is 12 ％ , and air hole distributings even, sample T 1 (gives out to see the picture of exterior form appearance of graph 1) only here, this kind of structure more profit grows air hole at bone organization inside, enhance the interfacial tie that cultivates body and matrix to spend, still can see numerous columnar the grain with grain shape, the diameter of grain is in 0.

5 ～ 2.

Inside limits of 5 μ M, the farther enlarge of these grain makes clear, they are by crystal of pettier accept rice HA (24 ～ 32nm) form, because petty grain can cause spectral line broaden, the XRD-LB standard that reason compares sample can be calculated dimension of brilliant of pink of coating giving HA, the average bead diameter of T 3 of actual measurement sample is 30nm. Faintness of the crystal boundary in T 4 coating is because of the reason with CaO overmuch impurity, and range of the crystal boundary in T 5 coating is more distinct, crystallization has been spent; The Ca/P that measures a powder of coating of T 2 sample is 1.

621, the Ca/P of it and person character is the most adjacent. We know, the main and main unit of the accept rice structure of bone is acicular with columnar HA crystal, they or directional and curly arrange, or mutual and intricate, form a variety of texture. The function that different texture forms bone to go up in accept rice dimension is unit, if bunchy structure and group agglomerate compose is comfortable at bearing high strenth, and curly and bunchy hand in scanty knit a structure to have very good tenacity, be helpful for nurture deliver. The corporeal composition administrative levels of this experimental HA powder is 3 levels, namely grain diameter is 30nm, they reunite to make an appointment with 100nm diameter particle, repass is intricate and ～ of knot synthesis 600nm the grain of diameter of 1 μ M (reunite body) , reunite have between body stronger intricate, pass observation of scanning report lens, reunite what body has parallel is columnar structure, be close to the structure of crude character. On the structure that integrates an interface in the HA coating of sample T1, T2, T3 and matrix and photograph of form appearance cover (2) seeing a picture hits a Ca, P and Ti a collection of illustrative plates, union is in in Ti radical composition of occurrence calcium phosphor, appear chemistry transfers layer, coating and matrix are physics and chemical union, its combine intensity to depend on the tensile strength of the HA crystal that agglomeration gives, it makes the combinative strength between coating and base rises greatly, place of law of plasma spray craft cannot accomplish this. Each parameter of sample T5 is most ideal, the coating thickness that measures a T 5 is 6 μ M about, measure so that the combinative strength of coating and base is 28MPa about. Adopt the measure that distilled water rinses, can reduce the content of oxidation calcium, but be in after repeating coating agglomeration 9 times, calcium carbonate appeared in sample (CaCO3) , its content as repeat a frequency to increase and increase, but preparation of fluid of collosol of the rest of place of coating of use last time is pulverous, do not have this kind of phenomenon however, this specification is worth constant collosol to PH, its chroma and composition are not followed deposit time change, the physical character that HA plays in average temperature and chemical composition are stable, by equivalent heat up: of formula of coefficient of expansion without directional crystal lattice?  / 20c0) 1/3 of α of L=(α 2c/ - 1, among them α and C are the crystal lattice constant below place need temperature, α 0, C0 is the crystal lattice constant in 25 ℃ . Can cipher out each temperature paragraph coefficient of expansion, be in normally before achieving 1150 ℃ , pure pottery and porcelain is the average with coefficient of expansion 13.

7 × 10 - 6 ℃ - 1 linear expands, but the structure that this won't destroy crystal, our firing temperature did not exceed besides 700 ℃ . When sample is impure, not only gel film has not stable oxidation calcium in agglomeration (CaO) appears, and the CO2 in air is mixed to sol fluid the sample in agglomeration process is influential also, be accumulated as a result of odd oxidation calcium additionally, such long in atmosphere agglomeration, will have gaseous hydride (CH4) and highest oxide (CO2) is generated, a variety of material are in high temperature for long to be able to produce physical change and chemical reaction, caCO3 should arise when CaO content is higher. The calcium carbonate of biology active pottery and porcelain of minim is contained in sample, can improve the physics of coating, chemistry and biology performance. Want to control the content of CaCO3, should maintain working environment cleanness, raise firing temperature appropriately, make CaCO3 decompose CaO and CO2 again, let sample every time immersing mediumly without ionic water time not less than 40min, idealer coating agglomeration number of plies is three-layer left and right sides, coating ply is in 6 μ of 3 ～ M limits. Graph the photograph of exterior form appearance of 1 sample T 1 (A) magnifies 700 times; (B) magnifies 5000 times Fig.

1The HA coating of 2 T1(a) of graph of Surface Form And Structure Of Sample T1, T2(b) , T3(c) and the structure that base integrates an interface and form appearance face (× 25000)Fig.

2Purity of preparation of 　 of conclusion of Form And Structure Of Combineed Interface Of Sample T1(a) , T2(b) , T3(c) 3, granuality, crystallization is spent and the combinative strength HA-Ti that all actors or actress cultivates style, be in for many times in the craft condition of coating agglomeration, deserve to compare except the raw material that notices the choice is right, outside value of sol fluid PH and constant temperature time, ply of affirmatory first-rate coating, repeat coating agglomeration frequency and firing temperature, be beneficial to raise HA-Ti compound the physics that cultivates style and chemical function. CNC Milling