CN108355165A - A kind of HA/MoS in titanium alloy surface with photocatalytic activity2The preparation method of biological composite coating - Google Patents
A kind of HA/MoS in titanium alloy surface with photocatalytic activity2The preparation method of biological composite coating Download PDFInfo
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Abstract
It is a kind of to prepare hydroxyapatite/molybdenum disulfide biological composite coating with photocatalytic activity in titanium alloy surface, assign coating excellent biocompatibility, osteogenic and photocatalysis antibacterial.HA/MoS is prepared first2Suspension is added dropwise suspension in the surfaces Ti6Al4V of polishing treatment with liquid-transfering gun after ultrasound, forms preset coating；Then laser treatment is carried out, is made strong bonded between preset coating and substrate.Finally by CVD stoves, vulcanizing treatment is carried out to the sample after laser melting coating, is prepared into HA/MoS2Biological composite coating.Its advantage is that：For the preparation method being combined by laser melting and coating technique and CVD other than so that coating and Ti6Al4V substrates is firmly combined with, the HA in coating can effectively play the advantage of biocompatibility, skeletonization and Integrated implant, meanwhile, the MoS in coating2Photocatalysis product, the effective oxidizing bacteria cell wall of energy and cell membrane can be generated by the irradiation of 660nm laser, destroy its DNA to make bacterium apoptosis.
Description
Technical field
The present invention relates to the interleaving techniques fields of material science and biomaterial, and specifically one kind is in titanium alloy surface
HA/MoS with photocatalytic activity2The preparation method of biological composite coating.
Background technology
Ti6Al4 as a kind of important titanium alloy, as implant material have excellent toughness, intensity and it is extensive
Apply and be implanted into surgical operation and shaping corrective procedure in bone.But since the inertia of its own cannot accelerate to promote bone tissue
It repairs, shortens recovery time, and the postoperative infection caused by the factors such as the external world frequently results in operative failure in implantation process,
Patient is forced to carry out second operation, this had both increased the pain of operation again of patient, and it is negative also to increase heavy economy to patient
Load.
So there is an urgent need for solve the problems, such as two aspect of bioactivity and antibacterial simultaneously for titanium alloy implant.And with Chinese
Fracture phenomenon caused by aggravation, traffic accident of mouth aging etc. increases, and the demand of bone implant material sharply increases.Therefore, research and development property
The excellent implant of energy, which just seems, to be increasingly urgent to.
The solution of implant biocompatibility is commonly relied on is made the compound painting of biology to the functional modification of material surface
Layer, or structure is conducive to the biological structure of cell adherence.But that there are binding forces is insecure for general biological composite coating, can not be long-term
The problem of being acted on host, and the regulation and control of biological structure prepare and accurate instrument are needed to carry out complicated fine operation.Although
There are many methods on solving implant antibacterial, such as take orally, injection of antibiotics, but these traditional antibiotic antibacterial means poles
It easily leads to bacterium and drug resistance occurs, induce the super drug resistance bacterium that any antibiotic can not all be eliminated.Therefore, it researches and develops while having
Standby superior bio compatibility, osteogenic, antibiotic property the implant of high combination property be very necessary and urgent thing.
Invention content
In order to solve technological deficiency, the present invention provides a kind of HA/MoS in titanium alloy surface with photocatalytic activity2
The preparation method of biological composite coating exists particular by laser melting coating with the method that chemical vapor deposition (CVD) is combined
Ti6Al4V alloy surfaces prepare the HA/MoS2 biological composite coatings with superior bio compatibility, osteogenic, antibiotic property.
First aspect present invention protects a kind of HA/MoS in titanium alloy surface with photocatalytic activity2The compound painting of biology
The preparation method of layer, steps are as follows includes：
S1, by HA and MoS2Powder mixes, and the HA/MoS that compound concentration is 1-200mg/mL2Then solution, ultrasound will
The mixed solution of acquisition obtains substrate surface with HA/MoS after being added dropwise to substrate surface, drying2The sample of precoated shet；
S2, Laser Cladding Treatment is carried out to the sample that step S1 is obtained so that the HA/MoS on substrate surface22Precoated shet with
Substrate is combined closely；
S3, after laser treatment in S2, the sample surfaces MoS of some2It has been oxidized to MoO3-X, therefore, take sulphur
The material mixing that powder is obtained with step S2, and chemical vapor deposition is carried out, with to HA/MoS2Surface carries out vulcanizing treatment, is made
Surface has HA/MoS2Biological composite coating.
The product that second aspect of the present invention protection first aspect the method prepares, i.e. titanium alloy surface are urged with light
Change active HA/MoS2Biological composite coating.
Third aspect present invention protects the second aspect coating in the application of implant antibiosis.
The beneficial effects of the invention are as follows：
(1) HA/MoS2 biological composite coatings can be firmly incorporated in Ti6Al4V implants using laser melting and coating technique
Surface makes coating have long-term stabilization on biocompatibility, osteogenic；
(2) the HA/MoS2 biological composite coatings of laser melting coating construct the surface body of hydrophilic scabrid hierarchical structure
System, this is extremely conducive to the adherency proliferation and differentiation skeletonization of cell.
(3) since the temperature of Laser Cladding Treatment is higher, the MoS in coating can be made2Decompose or be oxidized to MoO3-X, therefore,
CVD vulcanizing treatments are reused to prepare HA/MoS2 biological composite coatings after first laser melting coating so that the MoS in coating2It can
To generate photocatalysis product --- reactive oxygen species (ROS) by the irradiation of 660nm laser, the effective oxidizing bacteria of ROS energy is thin
Cell wall and cell membrane destroy its DNA to make bacterium apoptosis.
(4) raw material of HA and MoS2 used in this patent obtain convenient, will not induce bacterium and generate drug resistance, and price
It is cheap, it is easy to large-scale production and prepares HA/MoS2 biological composite coatings.
Description of the drawings
Fig. 1 is the HA/MoS2 (1 that after first laser melting coating prepared by CVD vulcanizing treatments in embodiment 1:1) biological composite coating
SEM figure；
Fig. 2 is HA/MoS2 (1 in embodiment 2:3) Raman spectrogram before and after CVD vulcanizing treatments；
Fig. 3 is that the antimicrobial flat-plate of the HA/MoS2 composite coatings of different proportion in embodiment 3 applies Butut；
Fig. 4 is the HA/MoS2 composite coatings surface Escherichia coli and staphylococcus aureus two of different proportion in embodiment 4
The SEM figures of kind bacterium pattern；
Fig. 5 is the MTT cytotoxicities detection figure of the HA/MoS2 composite coatings of different proportion in embodiment 5.
Specific implementation mode
A kind of HA/MoS in titanium alloy surface with photocatalytic activity2The preparation method of biological composite coating, step is such as
Under include：
S1, by HA and MoS2Powder mixes, and the HA/MoS that compound concentration is 1-200mg/mL2Then solution, ultrasound will
The mixed solution of acquisition obtains substrate surface with HA/MoS after being added dropwise to substrate surface, drying2The sample of precoated shet；
Preferably, in step S1, HA and MoS2Mass ratio be 1-100:1-100；
Preferably, in step S1, the ultrasound 0.5-2h in 500W or more ultrasonic machines；
Preferably, in step S1, the mixed liquor volume for being added dropwise to substrate surface is 10- 100uL；
Preferably, in step S1, dry concrete mode is：Surface, which is added dropwise, has the substrate of mixed liquor to be placed in baking oven,
And dry 0.3-3h under the conditions of 25-65 DEG C；
S2, Laser Cladding Treatment is carried out to the sample that step S1 is obtained so that the HA/MoS on substrate surface22Precoated shet with
Substrate is combined closely；
Preferably, in step S2, Laser Cladding Treatment, specially：Sample is positioned over two-dimensional laser platform, and laser electricity
Stream is 50-300A, frequency 5-100Hz, pulsewidth 0.1-20ms.
S3, due to after laser treatment in S2, the sample surfaces MoS of some2It has been oxidized to MoO3-X, therefore,
The material mixing for taking sulphur powder to be obtained with step S2, and chemical vapor deposition is carried out, with to HA/MoS2Surface carries out vulcanizing treatment,
Surface, which is made, has HA/MoS2Biological composite coating.
Preferably, in step S3, the quality of used sulphur powder is more than 0.2 times of HA and MoS2 gross masses on base coating.
Preferably, in step S3 steps, chemical vapor deposition, specially：Compounding substances are put into CVD tube furnaces, and
The heating parameter of CVD tube furnaces setting is 1-20 DEG C/min；Heating gradient is 25-900 DEG C, when reaction a length of 0.5-10h.
Preferably, in step S1-S3 steps, substrate is Ti6Al4V alloys.
To be best understood from the present invention, the present invention is done further be described in detail with reference to the accompanying drawings and examples, still
The scope of protection of present invention is not limited to the range of embodiment expression.
Embodiment 1：
A kind of HA/MoS in titanium alloy surface with photocatalytic activity2The preparation method of biological composite coating, step is such as
Under include：
S1, by the HA powder of 5mg and the MoS of 5mg2Powder mixes, and a concentration of 10mg/mL of deionized water configuration 1ml are used in combination
HA/MoS2Suspension (50%MoS2), then by ultrasound 1h in the suspension merging 600W power ultrasonic instrument of acquisition, then with shifting
Liquid rifle draws the HA/MoS of 50uL2Hanging drop is added to the surfaces Ti6Al4V, and is put into baking oven, dry under the conditions of 60 DEG C
1h, so that the surfaces Ti6Al4V are coated with HA/MoS2Precoated shet；
S2, two-dimensional laser platform is positioned over to the step S1 samples obtained, and it is 100A that laser current, which is arranged, frequency is
20Hz, pulsewidth 2ms carry out Laser Cladding Treatment；
S3, due to after laser treatment in S2, the surfaces the Ti6Al4V MoS of some2It has been oxidized to MoO3-X, because
This, the simple substance sulphur powder that the good sample of laser melting coating in step S2 is put into CVD tube furnaces, while weighing 0.3g is put into CVD pipes
In formula stove, the air in tube furnace is taken out and full of nitrogen as protective gas, and in CVD tube furnaces：Heating parameter is set as
10 DEG C/min, calefactive interzone is 50-750 DEG C, keeps 1h in 750 DEG C of conditions, so that it is fully reacted, finally naturally cool to room
Temperature.
The product obtained through the present embodiment carries out SEM scanning electron microscope detections, and the obtained SEM figures by low power to high power are (such as
Shown in Fig. 1, and figure is sequentially increased figure shown in amplification factor from a-b-c), testing result shows：50%MoS2The sample of amount applies
Layer surface has uneven scabrid structure, while the surface after vulcanization has the substance of sheet to be attached to sample surfaces so that
Sample surfaces form the surface system of hydrophilic scabrid hierarchical structure, this is extremely conducive to the adherency proliferation of cell and is divided into
Bone.
Embodiment 2：
A kind of preparation method that the prefabricated coating vulcanization of ratio is front and back is present embodiments provided, steps are as follows includes：
S1, by the HA powder of 2.5mg and the MoS of 7.5mg2Powder mixes, and is used in combination deionized water configuration 1ml a concentration of
The HA/MoS of 10mg/mL2Suspension (75%MoS2), then by ultrasound 1h in the suspension merging 600W power ultrasonic instrument of acquisition, so
The HA/MoS of 50uL is drawn with liquid-transfering gun afterwards2Hanging drop is added to the surfaces Ti6Al4V, and is put into baking oven, under the conditions of 60 DEG C
Dry 1h, so that the surfaces Ti6Al4V are coated with HA/MoS2Precoated shet；
S2, two-dimensional laser platform is positioned over to the step S1 samples obtained, and it is 100A that laser current, which is arranged, frequency is
20Hz, pulsewidth 2ms carry out Laser Cladding Treatment, then individually dispense a part of sample, and be labeled as 75%L-MoS2；
S3, due to after laser treatment in S2, the surfaces the Ti6Al4V MoS of some2It has been oxidized to MoO3-X, because
This, the another part not dispensed in step S2 is put by the sample of laser melting coating in CVD tube furnaces, while weighing 0.3g's
Simple substance sulphur powder is put into CVD tube furnaces, takes out the air in tube furnace and full of nitrogen as protective gas, and CVD tubular types
In stove：Heating parameter is set as 10 DEG C/min, and calefactive interzone is 50-750 DEG C, keeps 1h in 750 DEG C of conditions, keeps it fully anti-
It answers, finally naturally cools to room temperature, and the sample of acquisition is labeled as 75%S-MoS2。
The 75%L-MoS that the above method is handled2And 75%S-MoS2Sample carries out Raman spectrum test, obtains
The results are shown in Figure 2 for spectrum test, and testing result shows：Sample is in the MoS after laser melting coating2In S elements by O elements institute
Substitution, in 382 and 406cm-Without apparent Raman peaks at wavelength, and passes through CVD chemical vapor depositions and vulcanize 75%L-MoS2It is formed
75%S-MoS2Raman spectrum afterwards is in 382 and 406cm-There are strong and apparent Raman peaks at wavelength.Illustrate through laser melting coating and
CVD vulcanizing treatments are successfully prepared HA/MoS2Biological composite coating.
Embodiment 3：
Present embodiments provide the HA/MoS of different proportion2The preparation method and antibacterial effect of biological composite coating, step
Including：
S1、
S11, Ti6Al4V is polished polishing with the sand paper of 240 mesh, makes the one side of Ti6Al4V that mirror-like be presented；Then
Ultrasound is cleaned with ethyl alcohol 3 times, is then cleaned and is dried with deionized water, a part is used as experimental comparison group, another part to be used as
Following experiments use；
S12, by the HA powder of 5mg and the MoS of 5mg2Powder mixes, and a concentration of 10mg/mL of deionized water configuration 1ml are used in combination
HA/MoS2Suspension (50%MoS2), it is spare；
S13, the MoS for weighing 10mg2Powder prepares the HA/MoS of a concentration of 10mg/mL of 1mL with deionized water2(100%
MoS2) suspension, it is spare；
S14, by the HA/MoS of different ratio in step S12 and step S132Suspension is respectively put into 600w power ultrasonic instrument
Then middle ultrasound 1h draws the HA/MoS of 50uL with liquid-transfering gun2Hanging drop is added to the surfaces Ti6Al4V, and is put into 60 DEG C of baking ovens
Dry 1h, so that the surfaces Ti6Al4V are coated with HA/MoS2Precoated shet；
S2, two-dimensional laser platform is positioned over to the step S1 samples obtained, and it is 100A that laser current, which is arranged, frequency is
20Hz, pulsewidth 2ms carry out Laser Cladding Treatment；
S3, it will be put into CVD tube furnaces by the good sample of laser melting coating in step S2, while weigh the elemental sulfur of 0.3g
Powder is put into CVD tube furnaces, takes out the air in tube furnace and full of nitrogen as protective gas, and in CVD tube furnaces：Heating
Parameter is set as 10 DEG C/min, and calefactive interzone is 50-750 DEG C, keeps 1h in 750 DEG C of conditions, so that it is fully reacted, finally certainly
It so is cooled to room temperature, two obtained kind sample is respectively to contain 50%MoS2Sample
And 100%MoS2Sample.
S4, Ti6Al4V, 50%MoS by step S11 as a control group2Sample, 100%MoS2Sample be put into
In two 48 orifice plates, the Escherichia coli bacteria liquid of the 105CFU/mL of 400uL is added in one of orifice plate, another is equipped with mutually same
The staphylococcus aureus bacterium solution of the 105CFU/mL of 400uL is added in the orifice plate of product；
S5, by above-mentioned each added with the laser irradiation 15min of the hole of sample 660nm, laser parameter is set as, electric current
0.7A, distance 50cm；Then it takes the bacterium solution of 20uL to carry out tablet coating to count.
Bacterium colony counting is carried out to the tablet that the above method is handled, obtained tablet applies Butut as shown in figure 3, picture knot
Fruit shows：Tablet without laser melting coating and CVD the Ti6Al4V samples handled has a large amount of Escherichia coli and Staphylococcus aureus
Bacterium, and 50%MoS2Only fraction of two kinds of bacterial clumps, for 100%MoS2Sample still has two kinds of more bacteria livings,
But quantity will be less than the bacterial population of Ti6Al4V samples.Due to HA and MoS2By 1:It, can be by MoS after 1 ratio mixing2It is fixed on
In Ti6Al4V substrates, and 100%MoS2Sample is when carrying out laser melting coating since the high temperature that high-energy generates makes MoS2Easily
Volatilization.Illustrate 50%MoS by the result of tablet picture2Excellent resist all is shown to Escherichia coli and staphylococcus aureus
Bacterium property.
Embodiment 4：
Present embodiments provide the HA/MoS of different proportion2The preparation method and coating of biological composite coating are to bacterium pattern
Destruction, step includes：
S1、
S11, Ti6Al4V is polished polishing with the sand paper of 240 mesh, makes the one side of Ti6Al4V that mirror-like be presented, then use
Ethyl alcohol cleaning ultrasound 3 times, then uses deionized water cleaning, the dry substrate as coating, and be divided into three groups, spare；
S12, by the HA powder of 7.5mg and the MoS of 2.5mg2Powder mixes, and is used in combination deionized water configuration 1ml a concentration of
The HA/MoS of 10mg/mL2Suspension (25%MoS2), it is spare；
S13, by the HA powder of 5mg and the MoS of 5mg2Powder mixes, and a concentration of 10mg/mL of deionized water configuration 1ml are used in combination
HA/MoS2Suspension (50%MoS2), it is spare；
S14, by the HA powder of 2.5mg and the MoS of 7.5mg2Powder mixes, and is used in combination deionized water configuration 1ml a concentration of
The HA/MoS of 10mg/mL2Suspension (75%MoS2), it is spare；
S15, by the HA/MoS of different ratio in step S12, step S13 and step S142It is super that suspension is respectively put into 700W
Then ultrasound 1h in sound instrument draws the HA/MoS of 50uL with liquid-transfering gun respectively2Hanging drop is added to three groups of surfaces Ti6Al4V, and
60 DEG C of oven drying 1h are put into, so that the surfaces Ti6Al4V are coated with HA/MoS2Precoated shet
S2, two-dimensional laser platform is positioned over to the step S1 three groups of samples obtained, and it is 100A, frequency that laser current, which is arranged,
For 20Hz, pulsewidth 2ms, Laser Cladding Treatment is carried out；
S3, three groups of good samples of laser melting coating in step S2 are put into CVD tube furnaces, while to each merging CVD
The simple substance sulphur powder that 0.3g is added in sample in tube furnace takes out the air in tube furnace and full of nitrogen as protective gas,
And in CVD tube furnaces：Heating parameter is set as 10 DEG C/min, and calefactive interzone is 50-750 DEG C, keeps 1h in 750 DEG C of conditions, makes
It is fully reacted, and finally naturally cools to room temperature, and it is respectively 25%MoS to obtain three kinds of samples2, 50%MoS2And 75%MoS2。
S4, by three groups of samples：25%MoS2, 50%MoS2And 75%MoS2It is put into two 48 orifice plates, one of orifice plate
The Escherichia coli bacteria liquid of the 105CFU/mL of 400uL is added, the 105CFU/ of 400uL is added in another orifice plate equipped with same sample
The staphylococcus aureus bacterium solution of mL；
S5, by above-mentioned each added with the laser irradiation 15min of the hole of sample 660nm, laser parameter is set as, electric current
0.7A, distance 50cm；This bacterium solution Jing Guo laser irradiation is fixed again, it is thin to carry out SEM scannings after the processing such as dehydration
The pattern of bacterium.
The sample that the above method is handled after Bacteria Culture after carry out SEM scanning electron microscope detections, obtain SEM figures
As shown in Figure 4 (figure is followed successively by 25%MoS2,50%MoS2 and 75%MoS2 sample topography figure from a-b-c, similarly, d-e-f according to
Secondary is 25%MoS2,50%MoS2 and 75%MoS2 sample topography figure), testing result shows：Either Escherichia coli or gold
Staphylococcus aureus, in the doping with HA, MoS2Content it is higher, it is more serious to the destruction of bacteria cell wall.
Embodiment 5：
Present embodiments provide the HA/MoS of different proportion2The preparation method and coating of biological composite coating are to MC3T3-E1
The toxic effect of osteoblast, step include：
S1、
S11, Ti6Al4V is polished polishing with the sand paper of 240 mesh, makes the one side of Ti6Al4V that mirror-like be presented, then use
Ethyl alcohol cleaning ultrasound 3 times, then uses deionized water to clean, the dry substrate as coating, substrate of the part as coating, and one
Part uses as a control group；
S12, the HA powder by 10mg configure the HA suspension of a concentration of 10mg/mL of 1ml with deionized water, as
Control group is spare；
S13, by the HA powder of 7.5mg and the MoS of 2.5mg2Powder mixes, and is used in combination deionized water configuration 1ml a concentration of
The HA/MoS of 10mg/mL2Suspension (25%MoS2), it is spare；
S14, by the HA powder of 5mg and the MoS of 5mg2Powder mixes, and a concentration of 10mg/mL of deionized water configuration 1ml are used in combination
HA/MoS2Suspension (50%MoS2), it is spare；
S15, by the HA powder of 2.5mg and the MoS of 7.5mg2Powder mixes, and is used in combination deionized water configuration 1ml a concentration of
The HA/MoS of 10mg/mL2Suspension (75%MoS2), it is spare；
S16, the MoS by 10mg2The HA/MoS of a concentration of 10mg/mL of deionized water configuration 1ml is used in combination in powder2Suspension
(100%MoS2), it is spare；
S17, by the HA/MoS of different ratio in step S12, step S13, step S14, step S15, step S162It suspends
Liquid is respectively put into ultrasound 1h in 700W Ultrasound Instruments, then draws the HA/MoS of 50uL with liquid-transfering gun respectively2Hanging drop is added to five
The surfaces group Ti6Al4V, and 60 DEG C of oven drying 1h are put into, so that the surfaces Ti6Al4V are coated with HA/MoS2Precoated shet；
S2, two-dimensional laser platform is positioned over to the step S1 three groups of samples obtained, and it is 100A, frequency that laser current, which is arranged,
For 20Hz, pulsewidth 2ms, Laser Cladding Treatment is carried out；
S3, three groups of good samples of laser melting coating in step S2 are put into CVD tube furnaces, while to each merging CVD
The simple substance sulphur powder that 0.3g is added in sample in tube furnace takes out the air in tube furnace and full of nitrogen as protective gas,
And in CVD tube furnaces：Heating parameter is set as 10 DEG C/min, and calefactive interzone is 50-750 DEG C, keeps 1h in 750 DEG C of conditions, makes
It is fully reacted, and finally naturally cools to room temperature；
S4, five groups of samples that step S3 is obtained are respectively put into three identical 48 orifice plates, 400uL is added in the orifice plate
105CFU/mL MC3T3-E1 osteoblast liquid, cultivated respectively in 37 DEG C of incubators 1/3/7 day；According to MTT kits pair
Cell carries out Cytotoxicity evaluation.
Cytotoxicity detection detection, obtained result are carried out after cell culture to the sample that the above method is handled
As shown in figure 5, testing result shows：It compared with control group Ti6Al4V, either cultivates 1 day, 3 days or 7 days, tests sample
The activity of product group is all significantly larger than control group, illustrates that the sample prepared has nontoxic superior bio.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of HA/MoS in titanium alloy surface with photocatalytic activity2The preparation method of biological composite coating, feature exist
In：Steps are as follows includes
S1, by HA and MoS2Powder mixes, and the HA/MoS that compound concentration is 1-200mg/mL2Then solution, ultrasound will obtain
Mixed solution be added dropwise to substrate surface, it is dry after obtain substrate surface there is HA/MoS2The sample of precoated shet；
S2, Laser Cladding Treatment is carried out to the sample that step S1 is obtained so that the HA/MoS on substrate surface22Precoated shet and substrate
It combines closely；
S3, after laser treatment in S2, the sample surfaces MoS of some2It has been oxidized to MoO3-X, therefore, take sulphur powder with
The material mixing that step S2 is obtained, and chemical vapor deposition is carried out, with to HA/MoS2Surface carries out vulcanizing treatment, and surface is made
With HA/MoS2Biological composite coating.
2. method according to claim 1, it is characterised in that：In step S1, HA and MoS2Mass ratio be 1-100:1-100.
3. method according to claim 1, it is characterised in that：In step S1, the ultrasound 0.5-2h in 500W or more ultrasonic machines；
The mixed liquor volume for being added dropwise to substrate surface is 10-100uL.
4. method according to claim 1, it is characterised in that：In step S1, dry concrete mode is：Surface, which is added dropwise, to be had
The substrate of mixed liquor is placed in baking oven, and dry 0.3-3h under the conditions of 25-65 DEG C.
5. method according to claim 1, it is characterised in that：In step S2, Laser Cladding Treatment, specially：Sample is put
It is placed in two-dimensional laser platform, and laser current is 50-300A, frequency 5-100Hz, pulsewidth 0.1-20ms.
6. method according to claim 1, it is characterised in that：In step S3, the quality of used sulphur powder is more than base coating
Upper HA and MoS20.2 times of gross mass.
7. method according to claim 1, it is characterised in that：In step S3 steps, chemical vapor deposition, specially：It will mix
It closes substance to be put into CVD tube furnaces, and the heating parameter of CVD tube furnaces setting is 1-20 DEG C/min；Heating gradient is 25-900
DEG C, when reaction a length of 0.5-10h.
8. method according to claim 1, it is characterised in that：In step S1-S3 steps, substrate is Ti6Al4V alloys.
9. the HA/MoS for protecting any the method for claim 1 to 8 to prepare2Biological composite coating.
10. protecting coating described in claim 9 in the application of implant antibiosis.
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