Comprehensive Review of Preparation Methodologies of Nano Hydroxyapatite

P. Anitha1, Haresh M. Pandya2*

1 PG Department of Physics, Vellalar College for Women, Erode, India.2 Department of Physics, Chikkanna Government Arts College, Tirupur, India.

*Corresponding author: haresh.pandya@rediffmail.com

AbstractThe present paper provides a snapshot review of nano hydroxyapatite (HAP), its importance in biomedical and orthopedic fields and its various preparation methodologies. Most recent research related to these preparation methods are also reviewed comprehensively. Key words: Hydroxyapatite, sol gel, hydrothermal, microwave, ultrasonic, mechanochemical

1 Introduction

I t i s a well -es tabl ished fact tha t the Human bone consis ts of 20% of col legen f ibri ls , 69% of nano size crysta l l ine inorganic phase and 9% of water (Mollazadeh et al .2007; Nejal i e t al ) These Nano s ized crystal l ine composi te ingredients mainly resemble hydroxyapat i te (HAP) – Ca 1 0 (PO 4 ) 2 (OH) 2 basica lly a type of ca lc ium phosphate, wi th s t ructural dimensions s imilar to a rod or a needle ( length 40-60nm, width 10-20nm and thickness 1-3nm) (Luis C Mendes e t al . 2012). Further , i t i s also considered as one of the most s ignif icant human implantable mater ia ls on the basis of the degree of i ts biocompatibi l i ty , bioactivi ty and Osteroconduct ivity (Alessandra Bianco et al .2007). In addi t ion, i ts aff inity to create quick bonds with neighbor ing bones makes i t a lso a designer mater ial for bone repair or ar t i f ic ia l bone substi tute. The chemical , s tructura l and morphological propert ies of HAP bioceramic are highly sensi t ive to change in physical propert ies , chemical composi t ion and processing temperature .

Scient if ic l i te rature f inds ment ion of several methods of prepara t ion of Nano HAP. The most frequent ly used methods among these are

( i ) Co-Precipi tat ion Method (Zhang et al . 2003; Dan Nicolae Ungureanu a t a l . 2011; Ja inping Zhu e t al 2011; Luis C Mentes et al . 2012; Rozi ta Ahmad Ramil et al . 2011)

( i i ) Hydrothermal Method (Nasser Y Mustafa et al . 2011; Earl e t a l . 2006;

J ing Bing Liu e t al . 2003; Del ia et al . 2012; Mehmaz Salarian e t a l . 2008)

( i i i) Ul t rasonic Assis ted I rradia t ion Method ( Sahebal i Manaf i e t a l . 2008; Gerand Eddy Pioneer e t al . 2009; Kojima e t al . 2012; Eny Kusini e t a l . 2012; Coa Li Yun et a l . 2005)

( iv) Mechano Chemical Method (Tomohiro Iwasaki e t a l . 2011; Adzi la et a l . 2011; Radzal i Othman et al ; Yeong e t al 2001; Greta Gergely et al . 2010)

(v) Microwave Irradiat ion Method (Gobi et al . 2013; Siddharthan e t a l . 2005; Sahi l Ja lota et al . 2004; Mohammad Bhi lal Khan et a l . 2011; Samar kal i ta et al . 2010) and

(vi) Sol Gel method (Aldona e t al . 2006; Anbalagan et a l . 2006; Santosh e t al . 2009; Changsheng Liu et al . 2001; Khelendra Agarwal et al . 2011).

A review on most recent work done in these methods is provided below.

2 Nano Hydroxyapatite Preparation Methods

2.1 Co-Precipitation Method

This is the one of the most widely adopted methods due to i t s s implic i ty , rapid prepara tion as wel l as easy control of par t ic le s ize, composi t ion and var ious possibi l i t ies to modify overa l l homogenei ty of the product. The f i rs t s tage consis t of mixing the Anion solut ion e.g. calcium source with Cat ion solut ion e.g. phosphorous solut ion fol lowed by formation of nucleat ion, precipi ta t ion and f i l trat ion. The f ina l s tage consis ts of

calc inat ions under desi red temperature (Fig 1) . Table 1 shows the recent review of papers re la ted to Co-Precipi tat ion method in the las t two decades in this method. Due to

the s imul taneous occurrence of nuclea tion and crysta l growth, the react ion in this method requires a sharp f ine tuning to opt imize morphology and minimal crystal growth.

Table 1: Co Precipitation Method

2.2 Hydrothermal Method

This method involves the usage of water as a solvent heated in a sea led vessel . Table 2 shows the recent review of papers re la ted to the hydrothermal method

The ini t ia l s tage in the synthesis of Nano HAP in this method is choosing the Calc ium and Phosphorous precursor fol lowed by mixing the two by maintaining the Ca/P ra t io at a constant va lue of 1 .67 under hydrothermal reac tor mechanism (Fig 6) . The mixing is then al lowed to age, and subsequent ly washed and f i l te red. Final ly i t i s dried in an oven and calcined using muff le furnace . Table 2 shows the review of hydrothermal method work done in the last two decades.

The change in the solvent and reactant propert ies a t an extreme temperature means that experimental variables can be control led to a higher degree in this method. This regula tes the crysta l .

Table 2: Hydrothermal Method

2.3 Ultrasonic Irradiation Method

This method produces nano HAP by i rradia t ing the mixture of Ca Source and P (Fig 11) wi th a source of ul t rasonic radia tion of varying frequencies and power. The obtained mixture is a wel l-defined product wi th high pur ity . Table 3 highlights the recent review of papers related to this method. Physica l and chemical propert ies of the obtained mixture have been found to change with variat ion in frequency and power .

Mixing Ca and P precursor , maintaining Ca/P ra t io and pH as a constant value is the f i rs t and foremost s tep in the synthesis of Nano HAP by this method followed by the passage of ult rasonic waves of desi red frequency and power for a specif ic i rradia t ion t ime. Drying and calcinat ions are fol lowed by ul t rasonic t rea tment. Table 3 shows the review of ul trasonic i rradiat ion method work done from 2003 to 2012.

Table 3: Ultra sonic irradiation method

2.4 Mechano Chemical Method

The Mechano Chemical method is the combinat ion of mechanica l and chemical phenomena on a nano scale sol id mater ia l . Here nanomaterials are synthesized by mechanical act ivat ion and in this method, bal l mil l ing is a widely used technique wherein the powder mixture is placed in a bal l mil l and is subjected to high energy coll is ion from the bal ls and thus mechanical force is used to achieve chemical processing and t ransformat ion. Contaminat ion, long processing t ime, no control on part icle morphology, agglomerates , and residual s train in the crysta l l ized phase are the other disadvantages of high-energy bal l mil l ing process . However, the method is famous for i ts resul ts , var ious appl icat ions and potent ial scient i f ic va lues . Table 4 shows the recent review of papers re la ted to nano HAP with Mechano Chemical method

The method consis ts mainly of mixing Ca and P, maintaining Ca/P ra t io and pH (Fig 16) . The highl ight of this method is choosing a mechanical mill ing with selec ted mil l ing media such as Zirconia , agate , alumina ,

s ta inless s teel etc . with part icular speed and dura tion as wel l as cr i t ica lly maintaining the bal l mass rat io . The samples are given heat t rea tment. Table 4 shows the review of Mechano Chemical method work done in the las t two decades.

2.5 Microwave Assisted Irradiation Method

This method is one of the advanced methods for the prepara t ion of nano HAP with an associated disadvantage that the procedure is extended in compar ison with other methods. Microwave i rradiat ion provides an ef f icient , environmental ly f r iendly and economical ly viable method of heat ing due to i ts increased react ion kinet ics and rapid init ial heat ing coupled with reduced react ion t imes when compared to convent ional heat ing methods f ina lly culminating in products in powder form that a re wel l defined, of high puri ty and homogeneous. Table 5 shows the recent review of papers rela ted to microwave assis ted i rradia t ion method.

The usual s teps of mixing Ca+P, maintaining Ca/P rat io and pH are al l followed. The second step to be fol lowed is passing microwave radiat ion for a specif ic t ime fol lowed by heat t rea tment (Fig 21). Table 5 reviews work done in this method in the las t 20 years .

Table 5: Microwave Assisted Irradiation Method

2.6 Sol Gel Method

The Sol Gel method has of la te at t racted dedica ted at tent ion by a majori ty of researchers due to i t s many specia l features such as low tempera ture growth, low cost , homogeneous molecular products and the abi l i ty to produce nano sized par t ic les easily when compared with other methods. Table 6 shows the recent review of papers re la ted to Sol ge l method

The f i rs t s tep to be fol lowed in sol gel method is the choosing a Ca precursor and Phosphor precursor (Fig 26).The second s tep is mixing the above and f ixing the pH with ammonia or ammonium hydroxide , fol lowed by ageing, f i l t ra t ion, drying and ca lc inat ions. Table 6 shows the review of sol gel method work done in the las t 20 years .

.

Table 6: Sol Gel Method

3 CONCLUSION

In the present research art icle s ix di fferent methods for the prepara t ion of nano HAP have been descr ibed and the lates t research in those methods in the last two decades have also been reviewed.

Of the methods l is ted above with the ir varying methodologies , the authors fee l that the sol gel method is the s implest and easiest of the described methods to produce high puri ty , homogeneous nano HAP for subsequent usage in biomedical and or thopedic appl ica tions.

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