I would also consider using Electron Microscopy Techniques which will help characterise the structural composition of material from historical buildings. These techniques will help support both XRD and XRF analysis.   SEM for instance can provide both imaging and energy dispersive X-ray analysis of features.

SE and EDX analysis will also help you

Thank you for the feedbacks. But would it be necessary to have EDX and XRF? Is it not the same?

EDX will do elemental analysis a good system will now get you down to Boron  so there is more light element range with EDX. EDX being attached to the SEM will also allow you to concentrate on specific regions for analysis (phases/segregation) and with the right quant set up can provide reasonably good quantitative analysis.   Bare in mind that EDX technique is usually referred to as microanalysis whereas XRF is more bulk analysis.  Both EDX and XRF can relate to data produced by XRD so would be a good starting point.

This type of analysis is usually accomplished more easily by petrographic methods, which can include SEM/EDX when necessary. Find a concrete petrographer experienced in the analysis of historic materials. The petrographer can identify the components in the aggregates and binder and can perform modal analysis to estimate volume proportions of constituents. Simple calculations using assumed densities for the identified materials can provide proportions by mass.

I would not omit polarised light microscopy - cheap, effective and can provide much more information on internal structure, damage of the material, proportions, binder character etc.... it should be the first step

I absolutely agree with Katerina. The petrographer's basic tool is polarized-light microscopy.

I absolutely agree with Katerina. The petrographer's basic tool is polarized-light microscopy.

 I suggest reading an article from USP ( Universidade de São Paulo - Brazil ) , which describes a simple chemical method for reconstitution of the materials used . Follow the link: http://www.pcc.usp.br/files/text/publications/BT_00207.pdf.

Many laboratories perform simple chemistry: acid digestion. The results assume that all of the sand is insoluble and the binder is lime (or other materials depending on the rate of digestion). This method won't pick up hydraulic lime, Roman and natural cement, slag cement, and many other materials. Please examine ASTM C1324  for test chemical and petrographic methods to establish proportions of mortar components.

Referring to Laura's acid digestion and the occasionally wrong assumption that 'aggregate is acid-insoluble', see eg. the first case described in: Broekmans, MATM (2009): Petrography as an essential complementary method in forensic assessment of concrete deterioration: two case studies. Materials Characterization (60/7), Special Issue (35): 644-655.

The case could only be resolved using optical thin-section petrography.

How old is the building, and what is the purpose of the analysis?  Is it a concrete or masonry structure?   

Thank you all for the reply and sharings. Just some head ups, this building has been standing almost  200 years and a completely masonry structure. But throughout the years, some of the structures has been added and rectified without proper conservation techniques. So the idea is to identify the original material and design mix used plus investigating the mechanism of bricks deterioration because the structure seems to be degrading badly in some parts especially those have been in filled later. Petrography can actually be considered but the outputs has to be complementary to the rest of other testing which is the problem im having currently. I had problems analyzing the data which i think requires comparison analysis with previous studies of buildings around this area for a better understanding of the micro/macro morphology which also, in this case, could be a good pilot study for this particular case. However, i need to set some limitations. Not sure if this explains the whole idea of the study but i can share with you something dossier for those who is willing to help. Thanks 

Interesting background. Bricks can also be examined petrographically, but requires the petrographer to have some knowledge of what bricks are supposed to look like. Not all building material petrographers will have this knowledge (indeed, some don't really understand mortar). We often perform the ASTM C67 brick tests, especially absorption and saturation coefficient, to correlate with the petrographic studies. Even though C67 is for new brick the tests can still provide useful information. Damage to brick can be expected if the repair mortar is too strong so you might want to look at this first.

Interesting background. Bricks can also be examined petrographically, but requires the petrographer to have some knowledge of what bricks are supposed to look like. Not all building material petrographers will have this knowledge (indeed, some don't really understand mortar). We often perform the ASTM C67 brick tests, especially absorption and saturation coefficient, to correlate with the petrographic studies. Even though C67 is for new brick the tests can still provide useful information. Damage to brick can be expected if the repair mortar is too strong so you might want to look at this first.