CN101445931A - Microtextured implants and methods of making same - Google Patents

Abstract

The present invention concerns a microtextured implants and methods of making the same, concerns a process for etching metal by contacting the metal with a solution comprising hydrogen chloride and a persulfate salt; wherein the solution has a hydrogen chloride concentration of about 3 to about 11.7 moles/liter and a molar ratio of hydrogen chloride to persulfate salt of about 4:1 to about 134:1, wherein the persulfate salt is dissolved in the solution with the use of heat input.

Description

Microtextured implants and manufacture method thereof

Related application

The application requires to enjoy the right of priority that the sequence number that proposed on July 6th, 2007 is 60/958,492 U. S. application, and it is whole by with reference to being combined in this.

Invention field

The present invention relates to the method on a kind of solution etching metal surface that contains hydrogenchloride and persulphate, and with the microtextured implants of this method manufacturing.

Background of invention

Seek the segmental bone for a long time and replace graft many standards are arranged, comprise that (1) graft should keep patient's all one's life and do not lose function or cause any side effect reaction; (2) graft should make the normal function of its bone of transplanting recover; And (3) graft should be with the commercial size manufacturing.Satisfy above-mentioned standard, graft should be born the load that applies, and the contact surface of normally a kind of character of fluctuation, and graft and bone should bear the requirement of load.

A kind of plastic cement such as polymethylmethacrylate often are used to be attached on the bone graft to improve the consistency of graft and bone.The porous coating that holds with bone photo also often is used to graft, impels bone portion's growth within it, over time, repairs and makes the structural integrity of bone.The typical case of this dressing is disclosed in U.S. Patent number 3,855,638; 4,206,516; 4,156,943; 4,612,160.

Really, the validity of orthopedic implants usually depends on the existence of the irregular surface on the graft, and wherein bone can be grown between bone and graft and be formed natural connection.Existing several technology are used for creating irregular surface on graft.Sandblasting is a kind ofly to make shaggy technology, but the sandblasting meeting damages metal unit on the matrix top layer (as, pearl), and the significance that causes surface local to be dissected changes.Other mechanical coarse technology, as scrape or sanding, also be used.Also there is shortcoming in these technology, comprise the matrix distortion, remove too much material, can not or be difficult to make some surface irregularity, and the surface are coarse discontinuous.

Already used ceramic coating also has good effect, and usually desirable especially because between bone and stupalith such as the aluminium (aluminium sesquioxide) affinity is arranged.The typical case of this coating is disclosed in U.S. Patent number 4,145, and 764 and 4,483,678, particularly dental implant thing, and U.S. Patent number 4,309,488 and 4,846,837 discloses the bone alternate material that is used for whole body more widely.

Other work have utilized the height curved surface on the graft.U.S. Patent number 5,368,881 and 5,658,333 have shown the coatingsurface that uses non-spherical powder to make prosthese.

Some metal implants may are with the manufacturings of other cobalt-chromium-molybdenum of surgical grade (CoCrMo) alloy, and are good anticorrosive and wear-resistant because these alloys demonstrate.The CoCrMo surface energy of this alloy is by sandblast or by polishing medium such as aluminium and/or granulated glass sphere.Yet, by the sandblast machine roughening be a kind of can only be in the technology of visible surface operation, and can not make the hidden surface roughen on surface, as

Pearl.In addition, the polishing medium may be embedded between the pearl or remain in the metallic surface.

Used hydrogenchloride to carry out the microtexture (carbide, crystal boundary impurity) that chemical etching exposes CoCrMo.Yet chemical etching requires electric current to pass etched surfaces.This method be found can produce pearl neck crack or

The preferential etching that pearl connects does not reach the microtexture of satisfied bead surface.

Chemical milling usually relates to the use toxic reagent, and as methyl alcohol, or at high temperature (for example 80 ℃) use strong acid, or the mixture of strong acid.Chemical milling, even under these exacting terms, also need several hours to a few angel's surface irregularity.Also there is the trend of preferential etching crystal boundary in the method for these chemical millings, and this reduces the mechanical characteristic of graft.Chemical milling, for example, use 80% methyl alcohol and 20% be fuming hydrogenchloride (37%) at high temperature (70 ℃) be considered to exist safe reaction (Ferrari, M usually; Cagidiaco, M.C; Boracchini, A; Bertelli, E.The Joural of Prosthetic Dentistry, 1989,62 (5): p516-521).

Correspondingly, still needing can be in optimization that forms a kind of resulting structure surface on the metal or on the metal alloy matrix and method reliably.Also need to have the surgical plastic material of surface tissue.

Summary of the invention

On the one hand, the present invention relates to contain the solution of hydrogenchloride and a kind of persulphate; Wherein the concentration of hydrogenchloride is about 3 to about 11.7 mol in the solution, and the mol ratio of hydrogenchloride and persulphate is about 4: 1 to 134: 1; Wherein persulphate with heating for dissolving in solution.In addition, some embodiments contain the iron protochloride that exists with 0 to 3.5M amount.In some solution, persulphate be the concentration that exists in ammonium persulphate and preferred per 100 ml solns be 1 restrain 106 grams or, in some embodiments, be 1 to restrain 32 gram/per 100 ml solns.

The present invention also provides the method that comprises the following steps:

First solution that contains hydrogenchloride is provided, and wherein hydrogenchloride exists with the concentration of about 6 mol to about 12 mol;

First solution and second solution that contains persulphate and water are merged generation the 3rd solution; Wherein in second solution in per 100 ml waters the concentration of persulphate be 1 to 106 gram, and controlled temperature is at 15 ℃ to 100 ℃ between breaking-in period, and the volume ratio of first solution and second solution is that about 3:5 is to 30:1.

In some solution, the concentration of hydrogenchloride is 6 to 8 mol in first kind of solution.In some embodiment, first solution forms at ambient temperature.

Preferably, the volume ratio of first solution and second solution is that about 3:5 is ammonium persulphate or Potassium Persulphate to about 30:1 and/or persulphate.

In some preferred embodiment, second solution is to be contacted under 15 to 100 ℃ temperature with water and prepared by ammonium persulphate.In some preferred embodiments, second solution merges with first kind of solution under 15 to 100 ℃ temperature.

Method of the present invention can further comprise makes the 3rd solution contact the time that is enough to this metal of etching with a kind of metal object.Some method further comprise with this metal object from the 3rd solution, take out and water wash this metal object.In these embodiments, metal object contacts about 2 to about 60 minutes with the 3rd solution.Preferred metal object comprises at least a in cobalt, chromium and the molybdenum, as forging CoCrMo.

In a preferred embodiment, metal object contacts with a kind of acid solution before contacting with etching solution (for example, the 3rd solution).Metal object randomly is rinsed between various contacts.Metal object also can be dried after any contact or flushing.

Brief description of drawings

Fig. 1 has illustrated the figure of the etching power of the etch recipe of using 6N and 7N hydrogenchloride with figure.

Fig. 2 has shown that etched ASTM E1534 forges scanning electronic microscope (SEM) image of CoCrMo dish.

Fig. 3 has shown the SEM image of a kind of etched LCS knee joint femur CoCrMo porocoat (DePuy Cork) transplant.

Fig. 4 has shown and uses second kind of solution at the SEM image that is being with or without the etched knee joint type porocoat (CoCrMo) that makes under the control heating.

Fig. 5 has shown in the temperature of the second kind of solution that does not have the indoor conditions of controlled temperature (A) and prepare under 45 ℃ (B) and pH distribution.

Fig. 6 has shown etched

Pearl.The pitting (B) of the surface coverage 0.5 μ-2 μ size of each pearl.

The detailed description of illustrational embodiment

On the one hand, the invention describes the method for chemically etched metal object,, be used for forming the surface of microtexture as CoCrMo (for example, forging or casting alloy).The metallic surface of microtexture has shown can improve the fixing of bone fraction of coverage and terms of mechanics.

Some method of the present invention uses the saturated ammonium persulphate of heat activation as oxygenant.When preparation oxygenant (ammonium persulphate) solution when (second solution) application of heat be considered to form can be at etching reaction the time free radical, higher solvability and the heat energy of Geng Gao, everything all helps to be issued to repeatably and consistent etching microtexture in the condition of expense economy and safety.In some embodiments, second solution is 15-100 ℃, 15-85 ℃ or 20-60 ℃ or 30-50 ℃.In some embodiments, second solution can be used to form under the same temperature range of second solution and merge with first solution.

In some respects, invention disclosed provides under the condition (reduce acid concentration, and need not to preheat or indirect heating in etching process) of expense economy and safety on the CoCrMo plane or the porocoat bead surface reaches repeatably method with consistent etching microtexture.

First kind of solution (" acid mixture ") can pass through FeCl ₂Be dissolved in the hydrochloric acid and make.In some embodiments, hydrochloric acid (6-12N) can be randomly again with phosphoric acid (H ₃PO ₄) combination.In some embodiments, add phosphoric acid at ambient temperature.Typically, in acid mixture, add FeCl ₂To concentration be 20 to 1500ppm.The various concentration that comprise 12N that hydrochloric acid can be sold with the merchant.Phosphoric acid, the available various concentration that comprise 85wt% acid.Do not need further purifying when in some embodiments, acid is used.

Second solution can be by dissolving the persulphate preparation down at controlled temperature (15-100 ℃).Usually, second kind of solution contains 1 to 106 gram persulphate and 100 ml waters.In some embodiments, persulphate exists with 10-40 gram/100 ml waters.In an embodiment, second solution contains 32 gram persulphate and 100 ml waters.Persulphate, for example ammonium persulphate is commercially available.If desirable, salt does not need further purifying in use.

Here the ideal water for preparing solution can make in RO water.

The water that heating (passing through controlled temperature) can not need to add additional quantity during dissolving ammonium persulphate (oxygenant) makes the solubleness higher than room temperature preparation.Ammonium persulphate more high-dissolvability makes under acid (proton) concentration that is etched in minimizing and takes place.With interrelate theoretical different be to add thermogenesis persulfuric acid free radical (.SO during the dissolving ammonium persulphate ₄ ^-), this is than persulfuric acid ion (S ₂O ₄ ^2-) stronger oxygenant.This is considered to help to reach metal (for example, the CoCrMo) unanimity of bead surface microtexture.

The adding oxygenant (as, persulfate compounds) the help etching process.Yet, find that more multi-oxidizer does not always cause higher etching power.In fact too many oxygenant can suppress etching process.Unique relationships between the ratio of acid mixture and oxygenant is open and demonstration at this.Referring to Fig. 1.Be also noted that 2 equal prescriptions are used for etching CoCrMo and can reach same etching power, and the prescription of higher second solution of sour ratio can cause more heat to transfer to acid, making needs more substantial heating second solution when using.

Relate to metal object of the present invention and contain at least a of cobalt, chromium and molybdenum usually.Some objects contain each of cobalt, chromium and molybdenum.Some object is made by forging CoCrMo.In some embodiments, object is rosette or pearl.

In an embodiment, metal alloy is the F-75 type cobalt-chromium alloy (concrete standard is the casting alloy of casting of cobalt-28 chromium-6 molybdenum alloy and surgery transplant, and UNS R30075 specifies F75-01) of ASTM.In another embodiment, metal alloy is the F-1537 type cobalt-chromium alloy (concrete standard is the casting alloy of casting of cobalt-28 chromium-6 molybdenum alloy and surgery transplant, UNS R31537, UNSR31538, UNS R31539, appointment F1537-00) of ASTM.Exemplary materials typically contains the chromium of the 26-30% that has an appointment, the molybdenum of about 5-7% and isostatic cobalt.Can use another example of chrome-bearing alloy is stainless steel.Except chrome-bearing alloy, can use other examples of metal, it is stable in vivo, includes but not limited to titanium and titanium alloy.Those of ordinary skills can make the transplanting physical efficiency adopt it to use needed Any shape.

The biological medicine transplant that can form etched surface can be that a metallic element coating is attached to the metallic object at least a portion of metallic object outside surface.Metallic element can form three-dimensional porous surface geometry on the surface of metal biological medicine transplant.The metallic element of at least a portion is to be interconnected to form the hole (that is a matter hole) that connects between metallic element.The size range in these matter holes is from about 10 microns to about 200 microns, and in some cases up to 750 microns.Here, the transplant of this metallic element coating is meant " by porous coating ", and the metallic element coating is meant " Porocoat ".

The metallic element that forms porous coating can provide with any suitable form.Usually, metallic element comprises metallic particles, steel fiber, metal wire, or its combination.Metallic element can be arranged with predetermined pattern.For example, polybasic steel fiber or line can be aligned to one and throw the net, can be attached to the outside surface of metallic object.In a preferred embodiment, metallic element comprises metallic particles.More preferably, metallic particles comprises firm spherical metal pearl.These metallic particles or pearl can be any suitable size.Typically, the size of metallic particles or metallic bead is from about 40 microns to several millimeters.

Metal object (for example, CoCrMo disk) can be preheating to and be higher than room temperature (for example, using hot water).Metal object and acid mixture are added in the etching container.In acid mixture, add second solution then.The scope of second solution that adds in the etching container is (acid mixture): (second solution) ratio (v/v) from 2.5 to 100.

A potential advantage using second solution of heat is that it will heat passagely give acid when mixing, and does not therefore need to reheat acid and just makes and sourly be heated with secured fashion.

Typically, etching process continues 2-60 minute.In some embodiments, at CoCrMo

Produce the method for three-dimensional homogeneous microtexture (diameter of the depression of bead surface is 0.1 μ-10 μ) in the topography.

In some preferred embodiments, (for example, CoCrMo), before first solution and the merging of second persulfate solution, be immersed in the acid in advance.In some preferred embodiment, because persulphate and proton energy immediate response (our result shows that proton reduces immediately in the etching solution), the in advance immersion of metal in acid can be controlled etching process better.In some embodiments, the speed of the metal etch process of soaking in advance in the hydrogen chloride solution is faster.

In some embodiments, acid is soaked in advance and is carried out at least above 30 seconds.In some embodiment, the proton concentration of pre-soaking solution is about 1 to about 12 mol.In some embodiments, proton concentration is about 3 to about 12, about 4 to about 10, about 6 to about 9 mol.

The acid that can be used for pre-soaking comprises the mixture of haloid acid and haloid acid and oxygen acid.In some embodiments, pre-soaking solution comprises and contains the hydrochloric acid that concentration range is about 1 to 12 mol.In some embodiment, there is oxygen acid.A kind of suitable oxygen acid is a phosphoric acid, and it can exist to the concentration of 14 mol scopes with about 0.01M.Multiple other compound can be used in the etching solution as chloride compound.The typical concentration of compound is 0.01 to 2 mol like this.

The example of haloid acid includes, but are not limited to hydrogen fluoride, hydrogenchloride (hydrochloric acid), hydrogen bromide, and hydrogen iodide.In some embodiments, described haloid acid is that concentration range is that about 1M is to 12M; About 3.5M is to 8M; Hydrochloric acid with about 4.6M.

Oxygen acid has general formula H _aX _bO _c, wherein " a " represents the number of hydrogen atom, and " X " represents the element outside dehydrogenation or the oxygen, the number of " b " representative " X " atom, and the number of " c " represention oxygen atom.The example of oxygen acid includes but not limited to, nitric acid (HNO ₃), sulfuric acid (H ₂SO ₄), and phosphoric acid (H ₃PO ₄).In an embodiment, oxygen acid is that concentration range is that about 0.01M is to 14M; About 4M is to 8M; Phosphorated acid with about 5.6M.The phosphorated oxygen acid includes but not limited to, phosphorous acid, and peroxophosphoric acid, tetra-sodium, the peroxide tetra-sodium, triphosphoric acid, diphosphanetetroic acid, polyphosphoric acid, different diphosphanetetroic acid encircles three metaphosphoric acids, and phosphonic acids encircles four metaphosphoric acids, di 2 ethylhexyl phosphonic acid, poly-metaphosphoric acid, phospho acid and anhydrous oxygen acid.

Chlorine-containing compound contains chlorine, and there is a chlorine in the typical case.Most chlorine is salt, be by chlorine and metal directly in conjunction with or form by metal, metal oxide or a kind of mineral alkali and hydrochloric acid (aqueous solution of hydrogenchloride) reaction.The example of chlorine-containing compound includes but not limited to, sodium-chlor (NaCl), Repone K (KCl), calcium chloride (CaCl ₂), ammonium chloride (NH ₄Cl), iron(ic) chloride (FeCl ₃), or its mixture.In an embodiment, the concentration range of chlorine-containing compound is that about 0.01M is to 2M; About 0.6M is to 1.1M; With about 0.9M.

Before etching process began, stromal surface can be used typical common cleaning cleaning, as degreasing (as, chemistry, electrochemistry or electrolysis).Alternatively, can use other chemically cleaning operation, as using the basic solution cleaning.Stromal surface can be used the ultrasonic cleaning degreasing in washing composition, use ultrasonic cleaning then in the water of room temperature.The metallic surface that to clean contacts with the etching solution of suitable volumes in container or the pond then.The volume of etching solution depends on the surface-area of the etched matrix of wanting.In some instances, the whole surface-area of transplant is etched, so the volume of etching solution should be enough to not have whole transplant.In other were used, only some transplant was etched, has only the transplant of desired part to contact with etching solution.Those of ordinary skills can determine the volume of the needed etching solution of etching process at an easy rate.

Following definition is used to the complete understanding terminology used here.

As used herein, term " contact " or " contacting " mean puts together, directly or indirectly, a kind of composition or solution become physically approaching another kind of composition or solution.Contact can relate to two kinds of solution, two kinds of pure compounds, or a kind of pure compound and a kind of solution.

Terminology used here " mixture " means a kind of solution, suspension, dispersion liquid or emulsion." emulsion " is meant a kind of mixture of two or more common immiscible liquid, and normally a kind of colloidal form." suspension " or " dispersion liquid " is meant a kind of mixture, and preferably (for example, solid and liquid) disperses finely between two-phase or multiphase, preferably can keep stable in the time over a long time.

Term " envrionment temperature " tends to mean room temperature.In some embodiments, this temperature is 20 to 25 ℃.

The following example is used to explain the present invention, but can not be construed as limitation of the present invention.

Embodiment

Second solution

Second solution is that controlled temperature passes through down 120 gram (NH at 45 ℃ ₄) ₂S ₂O ₈Be dissolved in and be prepared from 150 ml waters.

Acid mixture

Acid mixture is by adding isopyknic hydrogenchloride (HCl), with the equivalent concentration of in each embodiment, mentioning, and phosphoric acid (85wt%) preparation.At hydrogenchloride with before phosphoric acid contacts, 0.2 gram FeCl ₂4H ₂O is added in the hydrogenchloride.

Disk

Bright finished ASTM F1537 forges the CoCrMo disk, and 3/4 inch of diameter is used among each embodiment.Such disk can with machinery from bar (ASTM F1537 forging) cut down and mirror polish after make (Ra＜0.1 μ).

The SEM image

The SEM image obtains (EFI company, Quanta FG 600) under the 20kV high vacuum.

Etching embodiment

Table 1 has listed in many experiments that the ratio of the equivalent concentration of hydrogenchloride and second solution and acid mixture changes in acid mixture.Acid mixture contains HCl acid (6-9N) and phosphoric acid (85%).Acid mixture contains 1 part of (volume) hydrogenchloride and 1 part of (volume) phosphoric acid.Second kind of solution is that controlled temperature is prepared from by 120 gram ammonium persulphates are dissolved in 150 milliliters of RO water under 45 ℃.In each embodiment, all there are weight saving and etching power.The bright finished ASTM F1537 of etching power by the per unit area that contacts with acid forges the weight saving of CoCrMo disk (3/4 inch of diameter) and determines.

Table 1

Embodiment	Etching period (minute)	The HCI equivalent	Second solution/acid mixture (v/v)	Weight saving (milligram)	Etching power (milligram/square inch)
						1	30	6	8/80	4.1	9.3
2	30	6	12/80	12.2	27.7
						3	30	6	16/80	1.6	3.6
4	30	6	32/80	0.5	1.2
						5	30	7	4/80	1.8	4.1
6	30	7	2/80	0.9	2.0
						7	30	7	4/80	1.2	2.7
8	30	7	8/80	4.6	10.4
						9	30	7	16/80	6.7	15.2
10	30	7	6/80	4.3	9.6
						11	30	7	8/80	4.3	9.7
12	30	7	16/80	17.6	39.8
						13	30	7	16/80	14.0	31.6
14	30	7	20/80	20.9	47.3
						15	30	7	24/80	19.3	43.7
16	30	7	32/80	1.5	3.4
						17	20	8	1/80	0.1	0.2
18	20	8	2/80	0.3	0.7
						19	20	8	4/80	2.2	5.0
20	20	9	8/80	3.7	8.4

Fig. 1 is with the figure of etching power of etch recipe that extracted data declaration in table 1.These curves disclose and do not had the highest etching power when highest oxidation agent (second kind of solution) concentration.Yet,, must use unique combination of second kind of solution/acid mixture ratio in order to obtain maximum etch power.

When use abundant etched hydrogenchloride and persulphate can be provided any than the time, in some embodiments, hydrogenchloride is that 4:1 is to 134:1 than the preferred molar ratio rate of persulphate.In other embodiment, ratio is from 5:1 to 19:1.

Embodiment 21

Shown among Fig. 2 that etched ASTM E1534 forges the SEM image of CoCrMo disk.Acid mixture contains 200ppm FeCl ₂4H ₂O and 85% phosphoric acid and hydrogenchloride (6 or 7N).The ratio of hydrogenchloride and phosphoric acid is 1:1 (v/v).Second kind of solution contains 120 gram ammonium persulphates in 45 ℃ 150 ml waters.(A) use 6N hydrogenchloride etching disk.The ratio of acid mixture and second kind of solution changes between the 40:1 at 10:4.(B) use 7N hydrogenchloride etching disk.The ratio of acid mixture and second kind of solution changes between the 40:1 at 5:1.Etch morphology changes according to the ratio of acid mixture and second kind of solution.

Embodiment 22

Fig. 3 has shown the SEM image of a kind of etched LCS knee joint femur CoCrMo porocoat (DePuy Cork) transplant.Acid mixture contains 200ppm FeCl ₂4H ₂O.Used 85% phosphoric acid and hydrogenchloride (6 or 7N), and the ratio of hydrogenchloride and phosphoric acid is 1:1 (v/v).Second solution contains 120 gram ammonium persulphates in 45 ℃ 150 ml waters.In Fig. 3, (A) and (B) be at the ratio (v/v) of acid mixture and second solution figure for 60 minutes knee joint femur of use 6N hydrogenchloride etching under the 10:1.(C) and (D) be that ratio (v/v) at the acid mixture and second solution is for using the figure of 30 minutes knee joint femur of 7N hydrogenchloride etching under the 10:2.The SEM image is with * 20,000 (B﹠amp; D) show etching microscopic dimensions (0.5-5 micron) form.The SEM image is with * 20,000 (A﹠amp; C) show that the microtexture form is at three-dimensional uniform distribution.

Embodiment 23

Fig. 4 has shown and uses second solution being with or without etched knee joint type porocoat (CoCrMo) the SEM image of making under the control heating.Room temperature (RT)-second solution does not have the preparation of controlled temperature ground under indoor conditions.When being dissolving, 45 ℃-second solution are controlled at that 45 ℃ of ground prepare in envrionment temperature (heating).(A) and (B) shown there be not preparation second solution under the temperature control, etch morphology all was uneven when etching period was 10 minutes to 30 minutes; (C) and (D) shown that being controlled at 45 ℃ in temperature prepares second solution down, etch morphology all was equally distributed when etching period was 10 minutes to 30 minutes.In this embodiment, second solution contains 2 gram NH ₄Cl and 4 gram (NH ₄) ₂S ₂O ₈With 12.5 ml waters.Acid mixture contains 20 milliliters of hydrogenchloride (12N), 20 milliliters of phosphoric acid (85wt%).

Embodiment 24

Fig. 5 has shown that indoor conditions (A) that does not have controlled temperature and the temperature of second solution for preparing and pH distribute under 45 ℃ (B).Second solution contains 2 gram NH ₄Cl and 4 gram (NH ₄) ₂S ₂O ₈With 12.5 ml waters.NH ₄Cl adds earlier in the entry, adds (NH then ₄) ₂S ₂O ₈

Embodiment 25 (table 2A-C)

The results are shown among the table 2A-C of etching metal disk.

The concentration of hydrogenchloride is 6-8N hydrogenchloride in first solution.0.2 gram FeCl ₂4H ₂O is added in 1 liter the hydrogenchloride and is stirred to dissolving fully.Among the embodiment in used first kind of solution hydrogen cloride concentration list in the table.

Second kind of solution is by adding (NH in 45 ℃ water in a double glazing warmer ₄) ₂S ₂O ₈And prepare, and the temperature of second kind of solution remains on 45 ℃ before use.The concentration of second kind of used solution is listed in the table among the embodiment.

Test plate is by following step pre-soaking.Bright finished forging CoCrMo test plate (ASTMF1537), 0.75 " diameter and 0.125 " thick, be attached

So that in being immersed in 80 milliliters (V1) first kind of solution the time, test plate has only a surface to expose on the material.Disk is immersed in first kind of solution 30 minutes.

After the pre-soaking, in first kind of solution, add second kind of solution etching disk of designated volume (V2), and etching disk 60 minutes.

Following definition is applied in the table:

V1: the volume of hydrogen chloride solution (first solution);

V2: the volume of ammonium persulfate solution (second solution)

[HCl]: the concentration of hydrogenchloride in the etching solution

[APS]: the concentration of ammonium persulphate in the etching solution

Weight loss: the difference of test plate weight before and after etching

Etching power: because the weight loss of the per unit surface-area that etching causes

Table 2A

The concentration of first solution (N)	The concentration of second solution (M)	The volume (milliliter) of V1 first solution	The volume (milliliter) of V2 second solution	V1:V2	[HCl] (N) in the etching solution	[APS] (M) in the etching solution	[H]/[APS] in the etching solution	Weight loss (milligram)	Etching power (milligram/square inch)
										8.0	2.97	80	4	20.0	7.62	0.14	53.9	7.5	16.9
8.0	2.97	80	8	10.0	7.27	0.27	26.9	20.2	45.7
										8.0	2.97	80	12	6.7	6.96	0.39	18.0	57.8	130.8
8.0	2.97	80	16	5.0	6.67	0.50	13.5	73.0	165.2
										8.0	2.97	80	20	4.0	6.40	0.59	10.8	78.4	177.4
8.0	2.97	80	24	3.3	6.15	0.69	9.0	65.1	147.3
										8.0	2.97	80	28	2.9	5.93	0.77	7.7	63.6	144.0
8.0	2.97	80	32	2.5	5.71	0.85	6.7	31.7	71.8
										8.0	2.97	80	36	2.2	5.52	0.92	6.0	27.3	61.9
8.0	2.97	80	40	2.0	5.33	0.99	5.4	16.8	38.1
										8.0	2.97	80	44	1.8	5.16	1.05	4.9	17.4	39.5
8.0	2.97	80	48	1.7	5.00	1.11	4.5	10.6	23.9
										8.0	2.97	80	2	40.0	7.80	0.07	107.7	1.1	2.4
8.0	2.97	80	50	1.6	4.92	1.14	4.3	8.1	18.3
										8.0	2.97	80	52	1.5	4.85	1.17	4.1	6.4	14.4
8.0	2.97	80	54	1.5	4.78	1.20	4.0	5.9	13.4
										8.0	2.97	80	56	1.4	4.71	1.22	3.8	6.9	15.5
8.0	2.97	80	60	1.3	4.57	1.27	3.6	4.6	10.3
										8.0	1.19	80	4	20.0	7.62	0.06	134.5	6.0	13.6
8.0	1.19	80	8	10.0	7.27	0.11	67.2	14.4	32.6
										8.0	1.19	80	12	6.7	6.96	0.16	44.8	21.4	48.4
8.0	1.19	80	16	5.0	6.67	0.20	33.6	26.3	59.5
										8.0	1.19	80	20	4.0	6.40	0.24	26.9	37.1	84.1
8.0	1.19	80	24	3.3	6.15	0.27	22.4	40.5	91.7
										8.0	1.19	80	28	2.9	5.93	0.31	19.2	32.1	72.8
8.0	1.19	80	32	2.5	5.71	0.34	16.8	18.6	42.1
										8.0	1.19	80	36	2.2	5.52	0.37	14.9	11.1	25.1
8.0	1.19	80	40	2.0	5.33	0.40	13.4	7.8	17.5
										8.0	1.19	80	44	1.8	5.16	0.42	12.2	5.3	11.9
8.0	1.19	80	48	1.7	5.00	0.45	11.2	3.3	7.5
										8.0	1.19	80	52	1.5	4.85	0.47	10.3	3.6	8.1

Table 2B

The concentration of first solution (N)	The concentration of second solution (M)	The volume (milliliter) of V1 first solution	The volume (milliliter) of V2 second solution	V1:V2	[HCl] (N) in the etching solution	[APS] (M) in the etching solution	[H]/[APS] in the etching solution	Weight loss (milligram)	Etching power (milligram/square inch)
										7.0	2.97	80	2	40.0	3.52	0.14	24.7	1.6	3.7
7.0	2.97	80	4	20.0	6.85	0.50	13.8	3.6	8.2
										7.0	2.97	80	8	10.0	16.35	1.33	12.3	13.0	29.4
7.0	2.97	80	12	6.7	28.64	1.92	14.9	35.4	80.2
										7.0	2.97	80	16	5.0	21.63	2.28	9.5	40.1	90.8
7.0	2.97	80	20	4.0	8.88	2.49	3.6	23.5	53.3
										7.0	2.97	80	24	3.3	6.13	2.63	2.3	22.2	50.3
7.0	2.97	80	28	2.9	1.48	2.71	0.5	7.1	16.0
										7.0	2.97	80	32	2.5	0.10	2.77	0.0	0.6	1.4
7.0	2.97	80	36	2.2	0.11	2.82	0.0	0.8	1.8

Table 2C

The concentration of first solution (N)	The concentration of second solution (M)	The volume (milliliter) of V1 first solution	The volume (milliliter) of V2 second solution	V1:V2	[HCl] (N) in the etching solution	[APS] (M) in the etching solution	[H]/[APS] in the etching solution	Weight loss (milligram)	Etching power (milligram/square inch)
										6.0	2.97	80	2	40.0	1.15	0.14	8	0.5	1.2
6.0	2.97	80	4	20.0	5.41	0.50	11	2.9	6.5
										6.0	2.97	80	8	10.0	6.66	1.33	5	5.3	12.0
6.0	2.97	80	12	6.7	0.13	1.92	0	0.2	0.4
										6.0	2.97	80	16	5.0	0.70	2.28	0	1.3	2.9
6.0	2.97	80	20	4.0	0.01	2.49	0	0.0	0.1
										6.0	2.97	80	24	3.3	0.03	2.63	0	0.1	0.2
6.0	2.97	80	28	2.9	0.01	2.71	0	0.1	0.2
										6.0	2.97	80	32	2.5	0.24	2.77	0	1.4	3.2
6.0	2.97	80	36	2.2	0.04	2.82	0	0.3	0.7
										6.0	2.97	80	40	2.0	0.01	2.85	0	0.1	0.3
6.0	2.97	80	44	1.8	0.06	2.87	0	0.7	1.6

Embodiment 26

CoCrMo PFC knee joint Porocoat is immersed in 80 milliliters of 8N hydrogenchloride in advance and (is contained 200ppm FeCl ₂4H ₂O) in 30 minutes, at 45 ℃ 4 milliliters of 2.97M persulfuric acid ammonium salts are added in the hydrogen chloride solution then.Phosphoric acid not in the prescription.Porocoat is etched 60 minutes.All Porocoat integument etchings make the pitting (Fig. 6 B) of the surface coverage 0.5 μ-2 μ size of each pearl.

Embodiment 27

The concentration of hydrogenchloride is 8N hydrogenchloride in the acid 1.0.2 gram FeCl ₂4H ₂O is added in 1 liter the hydrogenchloride and is stirred to dissolving fully.Acid 2 contains 8N hydrogenchloride.

Second solution is by adding (NH in 45 ℃ water in a double glazing warmer ₄) ₂S ₂O ₈And prepare, and the temperature of second solution remains on 45 ℃ before use.Second solution contains the 0.75M ammonium persulphate.

The bright finished forging CoCrMo test plate (ASTMF1537) on two-sided (two big surfaces), 0.75 " diameter and 0.125 " thick, be attached in perforation fully

On the material so that two of test plate glazed surfaces all expose in etching process.

(contain FeCl 80 milliliters of acid 1 ₂) in add 20 milliliter of second formulations prepared from solutions and obtain etching solution 1.(do not contain FeCl 80 milliliters of acid 2 ₂) in add 20 milliliter of second formulations prepared from solutions and obtain etching solution 2.

In order to react in etching solution 1, second solution (ammonium persulphate) is preceding adding, and test plate (each time point n=2) (contains FeCl 80 milliliters of acid 1 ₂) in pre-soaking 0,5,10 and 30 minutes.In order to react in etching solution 2, second solution (ammonium persulphate) is preceding adding, and test plate (each time point n=2) (does not contain FeCl 80 milliliters of acid 2 ₂) in pre-soaking 0,5,10 and 30 minutes.Table 3 has shown and has had Fe in the acid solution ²⁺When not having, etching power is higher.Add Fe ²⁺Additive method comprise iron or ferruginous compound be immersed in the acid to obtain dissolved Fe in acid ²⁺

Table 3 FeCl ₂With the effect of pre-soaking to etching power

EP (milligram/square inch)	0 minute	5 minutes	10 minutes	30 minutes
					Etching power
1	42.8+/-0.2	46.6+/-1.1	49.0+/-1.3	43.9+/-0.8
					Etching power 2	32.2+/-1.3	34.7+/-0.7	35.2+/-1.0	35.0+/-1.3

With acid 1 and second solution pre-mixing preparation in 5 minutes etching solution 3, add test plate then.Test plate (n=2) does not have in advance, and contact acid just is immersed in the etching solution 3.With acid 2 and second solution pre-mixing preparation in 5 minutes etching solution 4, add test plate then.Test plate (n=2) does not have in advance, and contact acid just is immersed in the etching solution 4.Table 4 has shown the etching power that reaches in two cases.

Table 4 pre-mixing is to the effect of etching power

EP (milligram/square inch)	Pre-mixing 5 minutes
		Etching power 3	0.1+/-0.0
Etching power 4	0.1+/-0.1

。

Claims (26)

1, a kind of etching solution that contains hydrogenchloride and persulphate; Wherein the concentration of hydrogenchloride is about 3 to about 11.7 mol in this solution, and the molar ratio of hydrogenchloride and persulphate is about 4: 1 to 134: 1; Wherein this persulphate is dissolved in the solution by heating.

2, the etching solution of claim 1 is gone back the iron protochloride of amount up to 3.5M in the described etching solution.

3, the etching solution of claim 1, wherein said persulphate is an ammonium persulphate.

4, the etching solution of claim 3, wherein said ammonium sulfate exists with the concentration of per 100 ml waters, 1 to 170 gram.

5, a kind of method comprises:

First solution that contains hydrogenchloride is provided, and wherein said hydrogenchloride is to exist with the concentration of about 6 mol to about 12 mol;

First solution and second solution that contains persulphate and water are merged generation the 3rd solution; Wherein the concentration of persulphate is per 100 ml waters, 1 to 170 gram in second solution, and this persulphate is dissolved in the water under 10 ℃ to 100 ℃ temperature, and the volume ratio of first solution and second solution is that about 3:5 is to about 30:1.

6, the method for claim 5, wherein the volume ratio of first solution and second solution is that about 3:5 is to about 30:1.

7, the method for claim 5, wherein said persulphate are ammonium persulphate or Potassium Persulphate.

8, the method for claim 5, wherein said persulphate is an ammonium persulphate.

9, the method for claim 8, wherein said second solution maintains the temperature at 20 ℃ to 70 ℃ preparations by ammonium persulphate is contacted with water under heating condition.

10, the method for claim 5, wherein the concentration of hydrogenchloride is 6 to 9 mol in first solution.

11, the method for claim 5, wherein first solution is to form under up to 100 ℃ envrionment temperature.

12, the method for claim 5, it further comprises makes the 3rd solution contact the time that is enough to this metal of etching with a kind of metal object; Described metal object has contacted in advance that a kind of to have proton concentration be about 1 to the acid solution of about 12 mol.

13, the method for claim 12, wherein the 3rd solution also contains the iron protochloride up to 3.5M in addition.

14, the method for claim 12, wherein said metal contact about 1 second to about 60 minutes with the 3rd solution.

15, the method for claim 12, wherein said metal with have the acid solution identical and contact with first strength of solution.

16, the method for claim 12, wherein said metal comprise at least a in cobalt, chromium and the molybdenum.

17, a kind of method of etching metal object, it comprise with described metal with

A kind of proton concentration is the about 1 acid solution contact to about 12 mol; With contact with a kind of etching solution; Described etching solution contains hydrogenchloride and persulphate; Wherein concentration is arranged is about 3 to the hydrogenchloride of about 11.7 mol to this solution, and the molar ratio of described hydrogenchloride and persulphate is that about 3:1 arrives about 135:1.

18, the solution of claim 17, wherein said persulphate is an ammonium persulphate.

19, the solution of claim 18, wherein said ammonium persulphate exists with the concentration of 170 grams/100 ml solns.

20, the method for claim 17, wherein said metal contact about 2 to about 60 minutes with etching solution.

21, the method for claim 17, wherein said metal comprise at least a in cobalt, chromium and the molybdenum.

22, the method for claim 17, wherein said etching solution is by comprising that following method makes:

First solution that contains hydrogenchloride is provided, and wherein said hydrogenchloride exists with the concentration of about 6 mol to about 12 mol;

First solution and second solution that contains persulphate and water are merged the generation etching solution; Wherein the concentration of persulphate is per 100 ml waters, 1 to 170 gram in second solution, and the volume ratio of first solution and second solution is that about 3:5 is to 30:1.

23, a kind of method comprises:

With metal and proton concentration is that about 1 solution A to about 12 mol contacts; With

With described metal and proton concentration is that about 3 solution B to about 11.7 mol contact, for persulphate, the ratio of hydrogenchloride and persulphate be about 4:1 to 134:1, and the concentration of iron protochloride is that 20ppm is to 3.5M.

24, the method for claim 23, wherein said iron protochloride is present in the solution A.

25, the method for claim 23, wherein when described metal contacted with solution A, described persulphate was added into solution A.

26, the method for claim 23, wherein the proton concentration of solution A is about 4 to about 10 mol.

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